TW201829362A - Compound, resin, composition, and method for forming pattern - Google Patents

Abstract

The invention provides a compound represented by the following formula (0), (in formula (0), R<SP>Y</SP> represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atom; R<SP>Z</SP> represents a N-valent group having 1 to 60 carbon atoms or a single bond; R<SP>T</SP> each independently represents an alkyl group having 1 to 30 carbon atoms which may have substitution, an aryl group having 6 to 30 carbon atom which may have substitution, an alkenyl group having 2 to 30 carbon atoms which may have substitution, an alkoxy group having 1 to 30 carbon atoms which may have substitution, a halogen atom, a nitro group, an amino group, a carboxyl group, a thiol group or a hydroxyl group, wherein said alkyl, aryl, alkenyl and alkoxy groups may contain an ether bond, a keto bond or an ester bond, and wherein at least one R<SP>T</SP> represents a hydroxyl group and at least one R<SP>T</SP> represents an alkenyl group having 2 to 30 carbon; X represents an oxygen atom, a sulfur atom, a single bond or is uncrosslinked; m each independently is an integer of 0 to 9, wherein at least one m is an integer of 2 to 9 or at least two m's are an integer of 1 to 9; N is an integer of 1 to 4, and when N is an integer of 2 or greater, the structural formulae included in N [ ]'s may be the same or different; and r each independently represents an integer of 0 to 2.).

Description

 Compound, resin, composition and pattern forming method  

The present invention relates to compounds having specific configurations, resins, and compositions containing the same. Further, the present invention relates to a pattern forming method using the composition.

In the manufacture of a semiconductor device, microfabrication using a lithography of a photoresist material is generally performed. However, in recent years, with the high integration and high speed of LSI, it is required to make the pattern rule more precise. . In addition, the source of the lithography used in the formation of the resist pattern can be expected to be short-wavelength from the KrF excimer laser (248 nm) toward the ArF excimer laser (193 nm), and extreme ultraviolet light (EUV) can also be expected. Import of 13.5 nm).

However, when the lithography of the conventional polymer-based resist material is used, the molecular weight is as large as 10,000 to 100,000, and the molecular weight distribution is also wide, and roughness is generated on the surface of the pattern, which makes it difficult to control the size of the pattern. There is a limit to the miniaturization. Here, in order to impart a resist pattern having higher resolution so far, various low molecular weight resist materials have been proposed. Since the low molecular weight resist material has a small molecular size, it is expected to provide a resist pattern having high resolution and low roughness.

A wide variety of such low molecular resistance materials are known. For example, a negative-type radiation-sensitive linear composition of a base-developing type using a low molecular weight polynuclear polyphenol compound as a main component (see, for example, Patent Document 1 and Patent Document 2) is proposed, and a low molecular weight resistance with high heat resistance is proposed. In the case of the candidate material, a negative-type radiation-sensitive linear composition having a low-molecular-weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1) is proposed. Further, in terms of the base compound of the resist material, it is known that the polyphenol compound is not only low molecular weight but also imparts high heat resistance, and is known to effectively improve the resolution or roughness of the resist pattern (refer to, for example, the non-patent literature). 2).

The inventors of the present invention have proposed a resist composition containing a compound having a specific structure and an organic solvent in terms of a material which is excellent in etching resistance and soluble in a solvent-soluble process (see, for example, Patent Document 4).

Further, since the refinement of the resist pattern progresses, problems such as resolution or collapse of the latent resist pattern may occur, and thus thin film formation of the resist is expected. However, if only the thin film of the resist is formed, it is difficult to obtain a sufficient film thickness of the resist pattern in the substrate processing. Therefore, it is not only a resist pattern but also a resist underlayer film formed between the resist-processed semiconductor substrate and the underlayer film in the resist film to have a function as a mask for processing the substrate.

Nowadays, various kinds of resist underlayer films for such processes are known. For example, unlike a resist underlayer film having a fast etching rate, a multilayer resist process containing a resin component and a solvent is proposed as a lower resist film for a lithography resist having a selectivity to a dry etching rate close to a resist. The underlayer film forming material is a substituent having at least a terminal group derived from a sulfonic acid residue by applying a predetermined energy (for example, refer to Patent Document 5). Further, as a resist underlayer film for lithography which has a selection ratio of a dry etching rate which is smaller than a resist agent, a resist underlayer film material containing a polymer having a specific repeating unit is proposed (for example, refer to Patent Document 6). . Further, as a lower film for lithographic resist having a selection ratio which is smaller than the dry etching rate of the semiconductor substrate, it is proposed to include a repeating unit copolymer of a repeating unit of a terpene and a substituted or unsubstituted hydroxyl group. A retardation underlayer film material of a polymer (for example, refer to Patent Document 7).

On the other hand, in the material of the resist underlayer film having high etching resistance, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas or acetylene gas in the raw material is known. However, from the viewpoint of the process, it is required to form a resist underlayer film material of a resist underlayer film by a wet process such as spin coating or screen printing.

In addition, the present inventors have proposed a composition for forming a lower layer film for lithography containing a compound having a specific structure and an organic solvent, which is excellent in etching resistance, high in heat resistance, soluble in a solvent, and suitable for a wet process. Material (for example, refer to Patent Document 8).

Further, as a method of forming the intermediate layer used in the formation of the resist underlayer film in the three-layer process, for example, a method of forming a tantalum nitride film (for example, refer to Patent Document 9) or a CVD formation of a tantalum nitride film is known. Method (for example, refer to Patent Document 10). Further, as a material for the intermediate layer for the three-layer process, a material containing a sesquiterpene oxyalkylene compound is known (for example, refer to Patent Documents 11 and 12).

There are various proposals for forming an optical component, for example, an acrylic resin (for example, refer to Patent Documents 13 to 14), or a polyphenol having a specific structure derived from an allyl group (for example, refer to Patent Document 15). )Been proposed.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-326838

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-145539

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-173623

[Patent Document 4] International Publication No. 2013/024778

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2004-177668

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-271838

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2005-250434

[Patent Document 8] International Publication No. 2013/024779

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2002-334869

[Patent Document 10] International Publication No. 2004/066377

[Patent Document 11] Japanese Laid-Open Patent Publication No. 2007-226170

[Patent Document 12] Japanese Patent Laid-Open Publication No. 2007-226204

[Patent Document 13] Japanese Patent Laid-Open Publication No. 2010-138393

[Patent Document 14] Japanese Laid-Open Patent Publication No. 2015-174877

[Patent Document 15] International Publication No. 2014/123005

 [Non-patent literature]  

[Non-Patent Document 1] T. Nakayama, M. Nomura, K. Haga, M. Ueda: Bull. Chem. Soc. Jpn., 71, 2979 (1998)

[Non-Patent Document 2] Okazaki Shinji and 22 other "new developments in the development of photoresist materials", CMC Publishing Co., Ltd., September 2009, p.211-259

As described above, there have been proposals for a lithographic film-forming composition for lithography for a large number of resist application orientations and a lithographic film-forming composition for the use of an underlayer film, but there is no applicable method other than spin coating. In the wet process such as screen printing, the high solvent solubility is also highly resistant to both heat resistance and etching resistance, and the development of novel materials is sought.

Further, in the past, many compositions in which optical members are oriented have been proposed. However, those having high heat resistance, transparency, and refractive index are not required, and development of novel materials has been sought.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a wet process which can be suitably used for forming a compound for an underlayer film for photoresist and photoresist which is excellent in heat resistance, solubility, and etching resistance. Resin and composition.

As a result of reviewing the above-mentioned problems, the inventors of the present invention have found that the above-described problems of the prior art can be solved by using a compound or a resin having a specific structure, and the present invention has been completed.

That is, the present invention is as follows.

[1] A compound represented by the following formula (0).

(In the formula (0), R ^Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and R ^{T is} independent of each other. An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent An alkoxy group of 1 to 30, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may further contain an ether bond or a ketone. a bond or an ester bond, wherein at least one of R ^T is a hydroxyl group, and at least one of R ^{T is} an alkenyl group having 2 to 30 carbon atoms, and X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, m Each is independent and is an integer from 0 to 9. Here, at least one of m is an integer of 2 to 9 or at least two of m are integers of 1 to 9, and N is an integer of 1 to 4, where N is When an integer of 2 or more is used, the structural formulae of N of [ ] may be the same or different, and r is independent of each other and is an integer of 0 to 2).

[2] The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (1).

(In the formula (1), R ⁰ is synonymous with R ^Y described above, R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently, and are a carbon number which may have a substituent. An alkyl group of ~30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, and a halogen An atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and here, R At least one of ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ^{5 is} an alkenyl group having 2 to 30 carbon atoms, and m ² and m ³ are each independently an integer of 0 to 8, m ⁴ and m ^{5 is} independent and is an integer from 0 to 9, except that m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ⁵ is 2 to 8 or 2 An integer of ~9 or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9, and n is synonymous with the above N. Here, when n is an integer of 2 or more, n The structural formulae in [ ] may be the same or different, and p ² to p ⁵ are each independent and are synonymous with the aforementioned r).

[3] The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the following formula (2).

(Formula 2) (, R ^0A line is synonymous with the R ^Y, R ^1A is n-1 to 30 carbon atoms of the divalent group ^A or a single bond, R ^2A independently, which may have a substituent group of a carbon number of 1 to 30 An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may further contain an ether bond, a keto bond or an ester bond, and here, R ^2A At least one of the hydroxyl groups, and at least one of R ^{2A is} an alkenyl group having 2 to 30 carbon atoms, and n ^A is synonymous with the above N. Here, when n ^A is an integer of 2 or more, n ^{A is} in [ ] The structural formulas may be the same or different, X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^2A are each independently an integer of 0-7, but at least one m ^2A is 2-7. An integer or at least two m ^2A are integers from 1 to 7, and q ^{A is} independent of 0 or 1).

[4] The compound according to [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1).

(In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the above, and R ⁶ to R ⁷ are each independently and may have The alkyl group having 1 to 30 carbon atoms of the substituent, the aryl group having 6 to 30 carbon atoms which may have a substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxyl group An acid group or a thiol group, wherein at least one of R ⁶ to R ^{7 is} an alkenyl group having 2 to 30 carbon atoms, and each of R ¹⁰ to R ^{11 is} independently a hydrogen atom, and m ⁶ and m ⁷ are each independently An integer from 0 to 7, except that m ⁴ , m ⁵ , m ⁶ and m ^{7 are} not 0).

[5] The compound according to [4], wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2).

(In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are synonymous with the above, R ⁸ to R ⁹ It is synonymous with R ⁶ to R ⁷ described above, and R ¹² to R ¹³ are synonymous with R ¹⁰ to R ¹¹ described above, and m ⁸ and m ⁹ are each independently, and are integers of 0 to 8, except m ⁶ , m ⁷ , m ⁸ And m ^{9 is} not 0).

[6] The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).

(In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are synonymous with the above, and each of R ^{3A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, and may have An aryl group having 6 to 30 carbon atoms of the substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein at least R ^3A One is an alkenyl group having 2 to 30 carbon atoms, and each of R ^{4A is} independently a hydrogen atom, and m ^{6A is} independently an integer of 0 to 5).

[7] A resin obtained by using the compound of [1] as a monomer.

[8] The resin according to [7], which has the structure shown by the following formula (3).

(In the formula (3), L may have a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms of a substituent, and an extended aryl group having 6 to 30 carbon atoms which may have a substituent. The alkylene group having a carbon number of 1 to 30 or a single bond may have a substituent, and the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and the R ⁰ system and R ^{Y is} synonymous, R ¹ is a n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently, and may have a substituent having an alkyl group having 1 to 30 carbon atoms and may have a substituent. An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid group a thiol group or a hydroxyl group, wherein the alkyl group, the aryl group, the alkenyl group and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and at least one of R ² to R ⁵ is a hydroxyl group. Further, at least one of R ² to R ^{5 is} an alkenyl group having 2 to 30 carbon atoms, and m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. ^{However, m 2, m 3, m} 4 and m ⁵ are not simultaneously ^{0, m 2, m 3,} m 4 and m ⁵ is an integer of at least 2 to 8 or 2 to 9 of m ^2, m ^3, at least two or an integer of 1 to 8, 1 to 9 of the m ⁴ and m ^5).

[9] The resin according to [7], which has the structure shown by the following formula (4).

(In the formula (4), L is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^0A is synonymous with the above R ^Y , and R ^1A is a carbon number of 1 to 30 n ^A The valence group or the single bond, R ^2A each independently, is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2~ An alkenyl group of 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, the aforementioned aryl group, and the aforementioned alkenyl group and the alkoxy group may contain an ether bond, ketone or ester linkages, herein, at least one of R ^2A is hydroxy, and R ^2A is at least one carbon atoms of the alkenyl group having 2 to 30, n ^a system with The above N is synonymous. Here, when n ^A is an integer of 2 or more, the structural formulas in n ^A of [ ] may be the same or different, and X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, m ^2A Independently, they are integers from 0 to 7, except that at least one m ^2A is an integer from 2 to 7 or at least two, m ^2A is an integer from 1 to 7, and q ^{A is} independent, and is 0 or 1).

[10] A compound represented by the following formula (0-A).

(In the formula (0-A), R ^Y' is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z' is an N-valent group or a single bond having 1 to 60 carbon atoms, R Each of ^{T' is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and may have The alkoxy group having 1 to 30 carbon atoms of the substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may also be used. Containing an ether bond, a ketone bond or an ester bond, wherein at least one of R ^{T ' is} an alkenyloxy group having 2 to 30 carbon atoms, and X' represents an oxygen atom, a sulfur atom, a single bond or no crosslink, m' Each of them is an integer of 0 to 9. Here, at least one of m' is an integer of 1 to 9, and N' is an integer of 1 to 4. Here, when N' is an integer of 2 or more, N' The structural formulas in [ ] may be the same or different, and r' is independent, and is an integer of 0 to 2).

[11] The compound according to [10], wherein the compound represented by the formula (0-A) is a compound represented by the following formula (1-A).

(In the formula (1-A), R ^{0 '} is synonymous with the above R ^{Y '} , and R ^{1 '} is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ^{2 '} to R ^{5 '} are each independently An alkyl group having 1 to 30 carbon atoms having a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1~ Alkoxy group of 30, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may further contain an ether bond, a ketone bond or An ester bond, wherein at least one of R ^{2 '} to R ^{5 ' is} an alkenyloxy group having 2 to 30 carbon atoms, and m ^{2 '} and m ^{3 '} are each independently an integer of 0 to 8, m ^{4 '} and m ^{5 'is} independent and is an integer from 0 to 9, except that m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0 at the same time, and n ' is synonymous with the aforementioned N', where n' is When an integer of 2 or more is used, the structural formulae in n [ ] may be the same or different, and p ^{2 '} ~ p ^{5 '} is synonymous with the aforementioned r).

[12] The compound according to [10], wherein the compound represented by the formula (0-A) is a compound represented by the following formula (2-A).

(In the formula (2A), R ^{0A 'line} with the R ^{Y' 'n A} is a single bond or a divalent group having a carbon number of 1 to 30, R ^2A' is synonymous, R ^1A is independently, which may have a substituent An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and an alkyl group having 1 to 30 carbon atoms which may have a substituent An oxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may further contain an ether bond, a keto bond or an ester bond. Here, at least one of R ^{2A′ is} an alkenyloxy group having 2 to 30 carbon atoms, and n ^A′ is synonymous with the above N. Here, when n ^A′ is an integer of 2 or more, n ^A′ is used [ The structural formulas within the formula may be the same or different, X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^2A' are each independently an integer of 0-7, but at least one m ^2A' For an integer from 1 to 7, q ^{A' is} independent of 0 or 1).

[13] The compound according to [11], wherein the compound represented by the formula (1-A) is a compound represented by the following formula (1-1-A).

(In the formula (1-1-A), R ^0' , R ^{1 '} , R ^{4 '} , R ^{5 '} , n, p ^{2 '} to p ^{5 '} , m ^{4 '} and m ^{5 '} are synonymous with the above, R ^6' to R ^7' are each independently, and are an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent. a group, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein R ^{10 '} to R ^{11 '} are each independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms, here, R ¹⁰ At least one of ^' ~R ^{11' is} an alkenyl group having 2 to 30 carbon atoms, and m ^6' and m ^7' are each independently an integer of 0 to 7, but m ^{4 '} , m ^{5 '} , m ^{6 '} and m ^{7' is} not 0 at the same time.

[14] The compound according to [13], wherein the compound represented by the formula (1-1-A) is a compound represented by the following formula (1-2-A).

(In the formula (1-2-A), R ^0' , R ^{1 '} , R ^6' , R ^7' , R ^{10 '} , R ^{11 '} , n ', p ^{2 '} ~ p ^{5 '} , m ^{6 '} and m ^{7 '} is synonymous with the above, R ^{8 '} ~ R ^{9 '} is synonymous with R ^{6 '} ~ R ^{7 '} , R ^{12 '} ~ R ^{13 '} is synonymous with R ^{10 '} ~ R ^{11 '} , m ^{8 '} and m ^{9 'is} independent, and is an integer from 0 to 8, except that m ^{6 '} , m ^{7 '} , m ^{8 '} and m ^{9 ' are} not 0).

[15] The compound according to [12], wherein the compound represented by the formula (2-A) is a compound represented by the following formula (2-1-A).

(In the formula (2-1-A), R ^0A' , R ^1A' , n ^A' , q ^A' and X ^{A' are the} same as defined above, and R ^3A' are each independently, and are carbon atoms which may have a substituent. An alkyl group of 1 to 30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group Here, R ^{4A' is} independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms. Here, at least one of R ^{4A' is} an alkenyl group having 2 to 30 carbon atoms, and m ^{6A' is} independent of each other. It is an integer from 0 to 5.)

[16] A resin obtained by using the compound of [10] as a monomer.

[17] The resin according to [16], which has the structure shown by the following formula (3-A).

(In the formula (3-A), the L system may have a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms of a substituent, and a carbon number of 6 to 30 which may have a substituent. a substituent having an alkylene group having 1 to 30 carbon atoms or a single bond, and the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may further have an ether bond, a keto bond or an ester bond, R ^{0 'The} system is synonymous with the above R ^{Y '} , R ^{1 '} is an n-valent group or a single bond having a carbon number of 1 to 60, and R ^{2 '} to R ^{5 '} are each independently, and are an alkane having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group And an amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may further contain an ether bond, a keto bond or an ester bond, and here, R ^{2 '} to R At least one of ^{5' is} an alkenyloxy group having 2 to 30 carbon atoms, and m ^2' and m ^3' are each independently an integer of 0 to 8, and m ^4' and m ^5' are each independently, and are 0 to 9 An integer, except that m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0).

[18] The resin according to [16], which has the structure shown by the following formula (4-A).

(In the formula (4-A), L' is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^0A' is synonymous with the above R ^{Y '} , and R ^1A' is a carbon number. 1 to 30 of the n-valent group ^a or a single bond, R ^{2A 'independently,} which may have an alkyl group having a carbon number of 1 to 30 substituted, the substituent group may have a carbon number of the aryl group having 6 to 30, may have a The alkenyl group having 2 to 30 carbon atoms of the substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, The aryl group, the alkenyl group and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^{2A′ is} an alkenyloxy group having 2 to 30 carbon atoms, and the n ^A′ system Synonymous with the above N, where n ^{A '} is an integer of 2 or more, the structural formulas in [ ] of n ^{A '} may be the same or different, and X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no cross. And m ^2A' are independent, and are integers of 0 to 7, except that at least one m ^2A' is an integer of 1 to 7, and q ^{A' is} independent of 0 or 1).

[19] A composition comprising: any one of [1] to [6] and any one of [7] to [9], and any one of [10] to [15] and [ One or more selected from the group consisting of any of the resins of 16] to [18].

[20] The composition according to [19], which further contains a solvent.

[21] The composition of [19] or [20], which further contains an acid generator.

[22] The composition according to any one of [19] to [21] which further contains a crosslinking agent.

[23] The composition according to [22] wherein the crosslinking agent is a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, or an acetylene urea. At least one selected from the group consisting of a compound, a urea compound, an isocyanate compound, and an azide compound.

[24] The composition of [22] or [23] wherein the crosslinking agent has at least one allyl group.

[25] The composition according to any one of [22] to [24] wherein the content of the crosslinking agent is 0.1 to 50% by mass based on the total mass of the solid component.

[26] The composition according to any one of [22] to [25] further comprising a crosslinking accelerator.

[27] The composition according to [26], wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.

[28] The composition of [26] or [27], wherein the content of the crosslinking accelerator is 0.1 to 5% by mass based on the total mass of the solid component.

[29] The composition according to any one of [19] to [28] which further contains a radical polymerization initiator.

[30] The composition according to any one of [19], wherein the radical polymerization initiator is a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo It is at least one selected from the group consisting of polymerization initiators.

[31] The composition according to any one of [19] to [30] wherein the content of the radical polymerization initiator is 0.05 to 25% by mass based on the total mass of the solid component.

[32] The composition according to any one of [19] to [31] which is used for the formation of a film for lithography.

[33] The composition according to any one of [19] to [31] which is used for the formation of a resist permanent film.

[34] The composition according to any one of [19] to [31], which is used for the formation of an optical component.

[35] A method for forming a resist pattern, comprising the steps of: forming a photoresist layer on a substrate using the composition of [32], irradiating a predetermined region of the photoresist layer with radiation, and performing development.

[36] A method for forming a resist pattern, comprising: forming an underlayer film on a substrate using the composition of [32], and forming at least one photoresist layer on the underlying film, after the photoresist The predetermined area of the layer is irradiated with radiation to perform a development step.

[37] A circuit pattern forming method comprising the steps of: forming an underlayer film on a substrate using the composition of [32], forming an interlayer film on the underlayer film using a resist interlayer film material, and a step of forming at least one photoresist layer on the intermediate layer film, irradiating a predetermined area of the photoresist layer with a radiation and developing a resist pattern, and forming the resist pattern as a mask to etch the middle portion The film is formed by etching the obtained underlayer film pattern as an etch mask as an etch mask, and using the obtained underlayer film pattern as an etch mask etching substrate, thereby forming a pattern on the substrate.

The compound of the present invention and the resin have high solubility in a safe solvent and are excellent in heat resistance and etching resistance. Further, the resist composition comprising the compound of the present invention and/or the resin imparts a good resist pattern shape.

 [Formation of the Invention]  

Hereinafter, the form of the present invention (hereinafter referred to as "this embodiment") will be described. Further, the following embodiments are illustrative of the invention, and the invention is not limited to the embodiments.

The compound, the resin, and the composition containing the resin in the present embodiment can be applied to a wet process, and can be effectively used for forming a photoresist underlayer film excellent in heat resistance and etching resistance. Moreover, the composition of the present embodiment can suppress the deterioration of the film at the time of high-temperature baking by using a compound or a resin having a high heat resistance and solvent solubility, and can form an etching resistance against oxygen plasma etching or the like. Also excellent resist and underlayer film. In addition, in the case where the underlayer film is formed, it is excellent in adhesion to the resist layer, and an excellent resist pattern is formed.

Further, since it has a high refractive index and can suppress coloring due to heat treatment in a wide range from low temperature to high temperature, it can be used as various optical forming compositions.

 [Compound represented by formula (0)]  

The compound in the present embodiment is represented by the following formula (0).

(In the formula (0), R ^Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and R ^{T is} independent of each other. An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent An alkoxy group of 1 to 30, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group may further contain an ether bond. a ketone bond or an ester bond, wherein at least one of R ^T is a hydroxyl group, and at least one of R ^{T is} an alkenyl group having 2 to 30 carbon atoms, and X represents an oxygen atom, a sulfur atom, a single bond or no crosslinking. m is independent and is an integer from 0 to 9. Here, at least one of m is an integer of 2 to 9 or at least two of m are integers of 1 to 9, and N is an integer of 1 to 4, where N When it is an integer of 2 or more, the structural formulae of N of [ ] may be the same or different, and r is independent of each other, and is an integer of 0 to 2).

R ^Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. As the alkyl group, a linear, branched or cyclic alkyl group can be used. R ^Y is an alkyl group having a carbon number of 1 to 30, a branched or cyclic alkyl group or an aryl group having 6 to 30 carbon atoms, and imparts excellent heat resistance and solvent solubility.

R ^Z is an N-valent group or a single bond having a carbon number of 1 to 60, and through this R ^Z , each aromatic ring is bonded. N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulae of N of [ ] may be the same or different. Further, the N-valent group means an alkyl group having 1 to 60 carbon atoms when N=1, an alkylene group having 1 to 60 carbon atoms when N=2, and a carbon number of 2 to 60 when N=3. An alkane propyl group, when N=4, is an alkane tetra group having a carbon number of 3 to 60. Examples of the above-mentioned N-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

R ^{T is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and may have The alkoxy group having 1 to 30 carbon atoms of the substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group may also be used. The ether bond, the ketone bond or the ester bond is contained. Here, at least one of the RTs is a hydroxyl group, and at least one of them is an alkenyl group having 2 to 30 carbon atoms. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

X represents an oxygen atom, a sulfur atom or no cross-linking, and when X is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and more preferably an oxygen atom. From the viewpoint of solubility, X is preferably a non-crosslinker. Further, m is independent and is an integer of 0 to 9, and at least two of m are integers of 1 to 9 or at least two of m are integers of 1 to 9.

In the formula (0), the moiety represented by the naphthalene structure has a monocyclic structure when r=0, a bicyclic structure when r=1, and a tricyclic structure when r=2. r is independent, and is an integer from 0 to 2. The above m can determine the range of values in accordance with the ring structure determined by r.

 [Compound represented by formula (1)]  

The compound (0) in the present embodiment is preferably a compound represented by the following formula (1) from the viewpoint of heat resistance and solvent solubility.

In the above formula (1), R ⁰ is synonymous with R ^Y described above, and is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. When R ⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, heat resistance is high, and solvent solubility tends to be improved. Further, from the viewpoint of suppressing oxidative decomposition and suppressing coloring of the compound and improving heat resistance and solvent solubility, R ⁰ is a linear, branched or cyclic alkyl group or carbon having 1 to 30 carbon atoms. A few 6 to 30 aryl groups are preferred.

R ¹ is a n-valent group or a single bond having a carbon number of 1 to 60, and each of the aromatic rings of R ¹ is bonded.

R ² to R ⁵ are each independently, and are an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent. An alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group which may have a substituent, the above alkyl group, the above aryl group, the above alkenyl group and the above alkoxy group group also containing an ether bond, ketone or ester linkages, herein, R ² ~ R ⁵ at least one hydroxyl group, and R ² ~ R ⁵ at least one of carbon atoms of the alkenyl group having 2 to 30.

m ² and m ³ are each independently, and are integers of 0 to 8, and m ⁴ and m ⁵ are each independently, and are integers of 0 to 9. However, m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ^{5 is} an integer of 2 to 8 or 2 to 9 or m ² or m ³ , At least two of m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9.

n is an integer from 1 to 4. Here, when n is an integer of 2 or more, the structural formulae in n of [ ] may be the same or different.

p ² to p ⁵ are each independently and have the same meaning as the above r, and are integers of 0 to 2.

Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

Further, the above-mentioned n-valent group means an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n=2, and a carbon number of 2 to 60 when n=3. An alkane propyl group, when n=4, is an alkane tetra group having a carbon number of 3 to 60. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Although the compound represented by the above formula (1) has a relatively low molecular weight, it has high heat resistance due to its structural rigidity, and therefore can be used even under high-temperature baking conditions. Further, the molecule has a grade 3 carbon or a grade 4 carbon, and the crystallinity is suppressed, and it is suitably used as a film for lithography used in the production of a film for lithography.

In addition, since the solubility in a safe solvent is high, heat resistance, and etching resistance are good, a composition for forming a lithography agent containing the compound represented by the above formula (1) can form a favorable resist pattern shape.

Furthermore, because of the lower molecular weight and low viscosity, even a substrate having a step (especially a fine pitch or a via pattern, etc.) can be easily uniformly filled to the corners of the step and the film flatness is improved. As a result, it was revealed that the composition was formed using the underlayer film by lithography, and the embedding and planarization characteristics were good. Further, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.

Further, since the aromatic density is high, the refractive index is high, and coloring is suppressed by heat treatment in a wide range from low temperature to high temperature. Therefore, it can be used as a composition for various optical components. Among them, a compound having a grade 4 carbon is preferred from the viewpoint of suppressing coloration by inhibiting oxidative decomposition of a compound and improving heat resistance and solvent solubility. In terms of optical parts, in addition to film-like and sheet-like parts, it can also be used as a plastic lens (稜鏡 lens, convex lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, A film for electromagnetic wave shielding, germanium, an optical fiber, a solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the above formula (1) is more preferably a compound represented by the following formula (1-1) from the viewpoint of ease of crosslinking and solubility in an organic solvent.

In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the above, and R ⁶ to R ⁷ are each independently and may have a substitution. An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxylic acid Or a thiol group, wherein at least one of R ⁶ to R ^{7 is} an alkenyl group having 2 to 30 carbon atoms, and R ¹⁰ to R ¹¹ are each independently a hydrogen atom, and m ⁶ and m ⁷ are each independently 0. An integer of ~7, except that m ⁴ , m ⁵ , m ^{6 ,} and m ^{7 are} not 0 at the same time.

Further, the compound represented by the above formula (1-1) is more preferably a compound represented by the following formula (1-2) from the viewpoint of easiness of further crosslinking and solubility in an organic solvent.

In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are synonymous with the above, and R ⁸ to R ⁹ are the above R ⁶ ~ R ⁷ is synonymous, R ¹² ~ R ¹³ lines above synonymous R ¹⁰ ~ R ^11, m ⁸ and m ⁹ each independently an integer of 0 to 8. However, m ⁶ , m ⁷ , m ⁸ and m ^{9 are} not 0 at the same time.

Further, the compound represented by the above formula (1-1) is preferably a compound represented by the following formula (1a) from the viewpoint of availability of a raw material.

In the above formula (1a), R ⁰ to R ⁵ , m ² to m ⁵ and n are synonymous with those described in the above formula (1).

The compound represented by the above formula (1a) is more preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.

In the above formula ^{(1b), R 0, R} 1, R 4, R 5, m 4, m 5 and n lines as in the above formula (1) described ^{synonymous, R 6, R 7, R} 10, R 11, The m ⁶ and m ⁷ systems are synonymous with those described in the above formula (1-1).

The compound represented by the above formula (1b) is more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.

In the above formula ^{(1c), R 0, R} 1, R 6 ~ R 13, m 6 ~ m 9 and n is synonymous with the lines in the above formula (1-2) is described.

Specific examples of the compound represented by the above formula (0) are shown below, but the compound represented by the formula (0) is not limited to the specific examples listed herein.

In the above formula, synonymous X-based as in the above-described formula (0) described, R ^{T 'lines} as in the above-described formula (0) described R ^T synonymous, R ^T' at least one is a hydroxyl group, and R ^{T 'at} least One is an alkenyl group having 2 to 30 carbon atoms. m is independent and is an integer of 0 to 9. Here, at least one of m is an integer of 2 to 9 or at least two of m are integers of 1 to 9.

Hereinafter, specific examples of the compound represented by the above formula (1) are exemplified, but are not limited thereto.

In the above formula, R ² , R ³ , R ⁴ and R ⁵ are synonymous with those described in the above formula (1), and at least one of R ² , R ³ , R ⁴ and R ⁵ is a hydroxyl group, and R ² and R are further. ^3, R ^4, R ⁵ and at least one of carbon atoms of the alkenyl group having 2 to 30. m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9. However, m ² , m ³ , m ⁴ , and m ^{5 are} not 0 at the same time.

The compound represented by the above formula (1) is excellent in the compound represented by the following formula (BiF-1) to (BiF-5) from the viewpoint of further solubility in an organic solvent.

In the above formula (BiF-1) to (BiF-5), R ^{6 '} to R ^{9 '} are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent An aryl group of 6 to 30, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein at least R ^{6 '} to R ^{9 '} One is an alkenyl group having 2 to 30 carbon atoms, and the R ¹⁰ to R ¹³ groups are synonymous with those described in the above formula (1c).

 [Compound represented by formula (0-A)]  

Further, the compound in the present embodiment is represented by the following formula (0-A).

(In the formula (0-A), R ^Y' is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z' is an N-valent group or a single bond having 1 to 60 carbon atoms, R Each of ^{T' is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and may have The alkoxy group having 1 to 30 carbon atoms of the substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group and the above alkoxy group may also be used. Containing an ether bond, a ketone bond or an ester bond, wherein at least one of R ^{T ' is} an alkenyloxy group having 2 to 30 carbon atoms, and X' represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, m' Each of them is an integer of 0 to 9. Here, at least one of m' is an integer of 1 to 9, and N' is an integer of 1 to 4. Here, when N' is an integer of 2 or more, N' The structural formulas in [ ] may be the same or different, and r' is independent, and is an integer of 0 to 2).

R ^Y' is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. As the alkyl group, a linear, branched or cyclic alkyl group can be used. R ^{Y '} is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and can impart excellent heat resistance and solvent solubility.

R ^Z' is a N-valent group or a single bond having a carbon number of 1 to 60, and each of the aromatic rings of the R ^{Z '} is bonded. When N' is an integer of 1 to 4, and N' is an integer of 2 or more, the structural formulae of N of [ ] may be the same or different. Further, the base of the above N' valence means an alkyl group having 1 to 60 carbon atoms when N' = 1, a alkyl group having 1 to 30 carbon atoms when N' = 2, and a carbon number of 2 when N' = 3 ~60 alkane propyl, N' = 4 is a carbon number of 3 to 60 alkane tetrayl. The base of the above N' valence may, for example, be a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the N'-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms.

R ^{T 'is} independently, and may be an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent. Alkoxy group having 1 to 30 carbon atoms having a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group, a hydroxyl group, the above alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group The ether bond, the ketone bond or the ester bond may be contained. Here, at least one of R ^{T '} is an alkenyloxy group having 2 to 30 carbon atoms. Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

X' represents an oxygen atom, a sulfur atom or no cross-linking, and when X' is an oxygen atom or a sulfur atom, it tends to exhibit high heat resistance, and more preferably an oxygen atom. From the viewpoint of solubility, X' is preferably a non-crosslinker. Further, m' is independent of each other and is an integer of 0 to 9, and at least one of m' is an integer of 1 to 9.

In the formula (0), the moiety represented by the naphthalene structure has a monocyclic structure when r' = 0, a bicyclic structure when r' = 1, and a tricyclic structure when r' = 2. r' is independent of each other and is an integer from 0 to 2. The above m' can be determined in accordance with the ring structure determined by r'.

 [Compound represented by formula (1-A)]  

The compound (0-A) in the present embodiment is preferably a compound represented by the following formula (1-A) from the viewpoint of heat resistance and solvent solubility.

(In the formula (1-A), R ^{0 '} is synonymous with the above R ^{Y '} , and R ^{1 '} is an n-valent group or a single bond having a carbon number of 1 to 60, and R ^{2 '} to R ^{5 '} are each independently An alkyl group having 1 to 30 carbon atoms having a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1~ An alkoxy group of 30, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group and the above alkoxy group may further contain an ether bond, a ketone bond or An ester bond, wherein at least one of R ^{2 '} to R ^{5 ' is} an alkenyloxy group having 2 to 30 carbon atoms, and m ^{2 '} and m ^{3 '} are each independently an integer of 0 to 8, m ^{4 '} and m ^{5 'is} independent and is an integer from 0 to 9, except that m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0 at the same time, and n ' is synonymous with N' above, where n' is When an integer of 2 or more is used, the structural formulae in n of [ ] may be the same or different, and p ^{2 '} ~ p ^{5 '} is synonymous with the above r).

Further, the alkyl group, the alkenyl group and the alkoxy group may be a linear, branched or cyclic group.

Further, the base of the above n' valence means an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n'=2, and a carbon number 2 when n'=3. 60 alkane propyl, n' = 4 is a carbon number of 3 to 60 alkane tetrayl. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Although the compound represented by the above formula (1-A) has a relatively low molecular weight, it can be used under high-temperature baking conditions because of its straight structure and high heat resistance. Further, since the molecule has a grade 3 carbon or a grade 4 carbon, the crystallinity is suppressed, and a composition for forming a film for lithography used in the production of a film for lithography can be used.

In addition, since the solubility in a safe solvent is high, and heat resistance and etching resistance are good, a composition for forming a lithography agent containing the compound represented by the above formula (1-A) can form a favorable resist pattern shape.

Furthermore, because of the lower molecular weight and low viscosity, even a substrate having a step (especially a fine pitch or a via pattern, etc.) can be easily filled uniformly to the corners of the step and the film is flattened. The results showed that the composition was formed using the underlayer film by lithography, and the embedding and planarization characteristics were good. Further, since it is a compound having a relatively high carbon concentration, high etching resistance can be imparted.

Further, since the aromatic density is high and the refractive index is high, and coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, it can be used as a composition for forming various optical components. Among them, a compound having a grade 4 carbon is preferred from the viewpoint of suppressing coloration by inhibiting oxidative decomposition of a compound and improving heat resistance and solvent solubility. In terms of optical parts, in addition to film-like and sheet-like parts, it can also be used as a plastic lens (稜鏡 lens, convex lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, A film for electromagnetic wave shielding, germanium, an optical fiber, a solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the above formula (1-A) is more preferably a compound represented by the following formula (1-1-A) from the viewpoint of ease of crosslinking and solubility in an organic solvent.

In the formula (1-1-A), R ^0' , R ^{1 '} , R ^{4 '} , R ^{5 '} , n, p ^{2 '} to p ^{5 '} , m ^{4 '} and m ^{5 '} are synonymous with the above, R ^{6 '} ~R ^{7' is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkenyl group having 2 to 30 carbon atoms which may have a substituent a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein R ^{10 '} to R ^{11 '} are each independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms, here, R ^{10 '} At least one of ~R ^{11 'is} an alkenyl group having 2 to 30 carbon atoms, and m ^6' and m ^7' are each independently an integer of 0 to 7, but m ^{4 '} , m ^{5 '} , m ^{6 '} and m ^{7' is} not 0 at the same time.

Further, the compound represented by the above formula (1-1-A) is further compounded by the following formula (1-2-A) from the viewpoint of easiness of further crosslinking and solubility in an organic solvent. good.

Specific examples of the compound represented by the above formula (1-2) are further exemplified as follows, but are not limited thereto.

In the above compound, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same as those described in the above formula (1-2), and R ¹⁰ to R ¹³ are each independently a hydrogen atom.

Specific examples of the compound represented by the above formula (2-1) are further illustrated below, but are not limited thereto.

In the above formulas, X is synonymous with the lines in the above formula (0) ^described, R ^{Y ',} R ^Z' lines as in the above-described formula (0) described R ^Y, R ^Z synonymous. Further, R ^{4A is} independently a hydrogen atom.

In the formula (1-2-A), R ^0' , R ^{1 '} , R ^6' , R ^7' , R ^{10 '} , R ^{11 '} , n ', p ^{2 '} ~ p ^{5 '} , m ^{6 '} and m ^{The 7'} line is synonymous with the above, R ^{8 '} ~ R ^{9 '} is synonymous with R ^{6 '} ~ R ^{7 '} , and R ^{12 '} ~ R ^{13 '} is synonymous with R ^{10 '} ~ R ^{11 '} , m ^{8 '} and m ^{9' is} independent, and is an integer from 0 to 8, but m ^6' , m ^7' , m ^8', and m ^{9' are} not 0 at the same time.

Further, the compound represented by the above formula (1-1-A) is more preferably a compound represented by the following formula (1a-A) from the viewpoint of the supply property of the raw material.

In the above formula (1a-A), R ^0' to R ^5' and m ^2' to m ^5' and n' are synonymous with those described in the above formula (1).

The compound represented by the above formula (1a-A) is more preferably a compound represented by the following formula (1b-A) from the viewpoint of solubility in an organic solvent.

In the above formula (1b), R ^{0 '} , R ^{1 '} , R ^{4 '} , R ^{5 '} , m ^{4 '} , m ^{5 '} and n ' are synonymous with those described in the above formula (1-A), and R ^{6 '} R ^{7 '} , R ^{10 '} , R ^{11 '} , m ^{6 '} and m ^{7 '} are synonymous as defined in the above formula (1-1-A).

The compound represented by the above formula (1b-A) is more preferably a compound represented by the following formula (1c-A) from the viewpoint of solubility in an organic solvent.

In the above formula (1c-A), R ^{0 '} , R ^{1 '} , R ^{6 '} to R ^{13 '} , m ^{6 '} to m ^{9 '} and n ' are synonymous with those described in the above formula (1-2-A). .

The compound represented by the above formula (1-A) is excellent in the compound represented by the following formula (BiF-1-A) to (BiF-5-A) from the viewpoint of further solubility in an organic solvent.

In the above ^formulas, R ^0, R ^1, n is synonymous with the system in the above formula (1-1) described, R ^{10 'and} R ^11' in line with the above formula (1-1) described in R ¹⁰ and R ¹¹ is synonymous R ^{4 '} and R ^{5 '} are each independently, and are an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 2 to 30 which may have a substituent. An alkenyl group, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the above alkyl group, the above aryl group, the above alkenyl group, The alkoxy group may further contain an ether bond, a ketone bond or an ester bond, and R ^{10 '} and R ^{11 '} are each independently a hydrogen atom. m ^{4 '} and m ^{5 '} are integers from 0 to 8, m ^{10 '} and m ^{11 '} are integers from 1 to 9, m ^{4 '} + m ^{10 '} and m ^{4 '} + m ^{11 '} are independent, respectively, from 1 to 9. The integer.

R ⁰ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl, phenyl, Naphthyl, anthracenyl, fluorenyl, biphenyl, and heptaphenyl.

R ^{4 '} and R ^{5 '} may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group or a fluorene group. , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, descending Borneol, adamantyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, olefin, methoxy, ethoxy, decane An oxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a thiol group.

Each of R ⁰ , R ^{4 '} and R ^{5 '} is exemplified to include an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkyl group having a carbon number of 1 to 30, and a carbon number of 6 An aryl group having a valence of ~30 or an alkenyl group having a valence of 2 to 30 carbon atoms.

R ¹⁶ may, for example, be methylene, ethyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and ten. Dienyl, nonenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclodecenyl, ring eleven Alkenyl, cyclododecenyl, cyclodecenyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent fluorenyl, divalent A mercapto group, a divalent biphenyl group, a divalent naphthylphenyl group, a divalent vinyl group, a divalent allyl group, and a divalent olefin group.

Each of the above R ¹⁶ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and each of R ^{14 is} independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and carbon. The aryl group of 6 to 30, or the alkenyl group having 2 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, and m ¹⁴ is an integer of 0 to 5. m ^{14 '} is an integer from 0 to 4, and m ¹⁴ is an integer from 0 to 5.

R ¹⁴ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl, cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, ven. Alkyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine atom , chlorine atom, bromine atom, iodine atom, thiol group.

R ¹⁴ in each of the above-described embodiment shown comprises isomers. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ⁰ , R ^4′ , R ^5′ , m ^4′ , m ^5′ , m ^10′ and m ^11′ are synonymous with the above, and R ^1′ is a group having 1 to 60 carbon atoms.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and each of R ^{14 is} independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and carbon. An aryl group of 6 to 30, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group, m ¹⁴ being an integer of 0 to 5, and m ^14' is 0~ An integer of 4, m ^14" is an integer from 0 to 3.

R ¹⁴ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl, cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, ven. Alkyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine atom , chlorine atom, bromine atom, iodine atom, thiol group.

Each of the above R ¹⁴ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6~. An aryl group of 30, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group.

R ¹⁵ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl or cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, ven. Alkyl, phenyl, naphthyl, anthracenyl, fluorenyl, biphenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine atom , chlorine atom, bromine atom, iodine atom, thiol group.

Each of the above R ¹⁵ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2).

The above compound is more preferably a compound shown below from the viewpoint of availability of a raw material.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2).

Further, the compound represented by the above formula is more preferably a compound represented by the following structure from the viewpoint of etching resistance.

In the above formula, R ^0A is synonymous with the above formula R ^Y , R ^1A′ is synonymous with R ^Z , and R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2). R ¹⁴ each independently, a carbon number of 1 to 30 linear, branched, or cyclic alkyl group of 6 to 30 carbon atoms, an aryl group, an alkenyl group or a C number of 2 to 30, 1 to 30 carbon atoms The alkoxy group, the halogen atom, and the thiol group, and m ^14' is an integer of 0 to 4.

R ¹⁴ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl, cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, adamantane Base, phenyl, naphthyl, anthracenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine, chlorine, bromine, iodine Atom, thiol group.

Each of the above R ¹⁴ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2), and R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and a carbon number of 6~. An aryl group of 30, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom or a thiol group.

R ¹⁵ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl or cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, adamantane Base, phenyl, naphthyl, anthracenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine, chlorine, bromine, iodine Atom, thiol group.

Each of the above R ¹⁵ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and R ¹⁶ is a linear, branched or cyclic alkyl group having a carbon number of 1 to 30, and a carbon number of 6 An aryl group having a valence of ~30 or an alkenyl group having a valence of 2 to 30 carbon atoms.

R ¹⁶ may, for example, be methylene, ethyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and ten. Dienyl, nonenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclodecenyl, ring eleven Alkenyl, cyclododecenyl, cyclodecenyl, divalent norbornyl, divalent adamantyl, divalent phenyl, divalent naphthyl, divalent fluorenyl, divalent Heptaphenyl, a divalent vinyl group, a divalent allyl group, and a divalent olefin group.

Each of the above R ¹⁶ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2), and each of R ^{14 is} independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms and carbon. 6 to 30 of the aryl group, an alkenyl group or a C number of 2 to 30, carbon atoms, an alkoxy group of 1 to 30, a halogen atom, a thiol group, m ¹⁴ represents an integer of 0 to 5.

R ¹⁴ may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, decyl, cyclopropyl. , cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclodecyl, norbornyl, adamantane Base, phenyl, naphthyl, anthracenyl, heptaphenyl, vinyl, allyl, olefinic, methoxy, ethoxy, decyloxy, fluorine, chlorine, bromine, iodine Atom, thiol group.

Each of the above R ¹⁴ is exemplified to contain an isomer. For example, butyl includes n-butyl, isobutyl, sec-butyl, tert-butyl.

In the above formula, R ¹⁰ to R ¹³ are the same as those described in the above formula (1-2).

The compound represented by the above formula is preferably a compound having a dibenzoxanthene skeleton from the viewpoint of heat resistance, and is more preferably represented by the following structure from the viewpoint of raw material availability.

In the above formula, R ^0A is synonymous with the above formula R ^Y , R ^1A′ is synonymous with R ^Z , and R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2).

The compound represented by the above formula is preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.

In the above formula, R ¹⁰ to R ¹³ are synonymous with those described in the above formula (1-2), and R ¹⁴ , R ¹⁵ , R ¹⁶ , m ¹⁴ and m ^14' are synonymous with the above.

 [Method for Producing Compound of Formula (0) and Method for Producing Compound of Formula (0-A)]  

The compound represented by the formula (0) and the compound represented by the formula (0-A) in the present embodiment can be suitably synthesized by a conventional method, and the synthesis method is not particularly limited. Hereinafter, a method for producing a compound represented by the formula (0), a method for producing a compound represented by the formula (0-A), a method for producing a compound represented by the formula (1), and a formula (1-A) will be exemplified. A method of producing a compound.

For example, under normal pressure, a polyphenol compound is obtained by polycondensation reaction of a biphenol, a binaphthol or a hydrazine phenol with a corresponding ketone under an acid catalyst, followed by at least one polyphenol compound. The phenolic hydroxyl group is introduced into the allyl group to give a compound represented by the formula (1-A). Thereafter, the compound represented by the formula (1) can be obtained by heating the compound represented by the formula (1-A) to recombine Kreisen. These reactions can be carried out under pressure as needed.

The timing of introducing the allyl group can be introduced after the production of the resin in the pre-stage, the post-stage of the condensation reaction or later.

Examples of the above-mentioned biphenols include biphenol, methyl biphenol, and methoxy binaphthol, and are not particularly limited. These may be used alone or in combination of two or more. Among these, from the viewpoint of the stability of the raw material supply, it is more preferable to use a biphenol.

Examples of the binaphthols include, for example, binaphthol, methyl binaphthol, and methoxy binaphthol, and are not particularly limited. These may be used alone or in combination of two or more. Among these, from the viewpoint of increasing the carbon atom concentration and improving the heat resistance, it is more preferable to use binaphthol.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornrone, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzene. Anthrone, anthraquinone, ethane naphthone, anthracene, acetophenone, diethyl benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, Diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoneone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. It is not particularly limited by these. These may be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornone, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzopyrene are used. Ketone, anthraquinone, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl a carbonyl biphenyl, a benzophenone, a diphenylcarbonylbenzene, a triphenylcarbonylbenzene, a benzonaphthone, a diphenylcarbonylnaphthalene, a phenylcarbonylbiphenyl group, a diphenylcarbonylbiphenyl group, preferably. From the standpoint of improving etching resistance, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl is used. Phenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoneone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are more preferred.

In terms of ketones, from the viewpoint of having both high heat resistance and high etching resistance, it is preferred to use an aromatic ketone.

The acid catalyst used in the above reaction can be appropriately selected and used from a conventional one, and is not particularly limited. As such an acid catalyst, inorganic acids or organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen bromide acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid. , azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonate An organic acid such as acid or naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. The solid acid or the like is not particularly limited as such. Among these, from the viewpoint of production, it is preferable to use an organic acid and a solid acid, and it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of ease of manufacture or ease of handling. . Further, the acid catalyst may be used singly or in combination of two or more. In addition, the amount of the acid catalyst to be used is appropriately determined depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited, and is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. It is better.

In the case of the above reaction, a reaction solvent can also be used. The reaction solvent can be carried out by using a reaction of a ketone with a biphenol, a binaphthol or a hydrazine diol, and is not particularly limited, and can be appropriately selected and used by a person skilled in the art. The reaction solvent may, for example, be water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the reaction solvent to be used may be appropriately set depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited, and is 0 to 2000 based on 100 parts by mass of the reaction raw material. The range of parts by mass is preferred. Further, the reaction temperature in the above reaction can be appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, and is usually in the range of 10 to 200 °C.

In order to obtain a polyphenol compound, the reaction temperature is preferably higher, and specifically, it is preferably in the range of 60 to 200 °C. In addition, the reaction method can be appropriately selected from the conventional methods, and is not particularly limited, and examples thereof include a method of adding a biphenol, a binaphthol or a hydrazine diol, a ketone, or a catalyst at a time, or a bisphenol. A method in which a class, a binaphthol or a hydrazine diol or an aldehyde or a ketone is dripped in the presence of a catalyst. After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out by a general method, and is not particularly limited. For example, in order to remove unreacted raw materials, catalysts, and the like which are present in the system, it is possible to separate by using a general method of increasing the temperature of the reaction vessel to 130 to 230 ° C and removing volatiles at about 1 to 50 mmHg. A compound as a target.

The preferred reaction conditions include the use of a phenol, a binaphthol or a hydrazine diol, a molar amount of excess of 0.001 to 1 mole, and an acid catalyst. It is allowed to react at 50 to 150 ° C for 20 minutes to 100 hours under normal pressure.

After the reaction is completed, the object can be isolated by a conventional method. For example, the reaction solution is concentrated, pure reaction water is added, and the reaction product is precipitated. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid matter is filtered and dried, and then subjected to column chromatography and by-products. The compound represented by the above formula (1) can be obtained by separation and purification, solvent distillation, filtration, and drying.

Further, a method of introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.

For example, as described below, an allyl group can be introduced into at least one phenolic hydroxyl group of the above compound.

The compound for introducing an allyl group can be synthesized or easily obtained by a conventional method, and examples thereof include allyl chloride, allyl bromide, and allyl iodide, but these are not particularly limited. .

First, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, it is allowed to react at normal pressure and at 20 to 150 ° C for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid, added to distilled water to precipitate a white solid, and the separated solid is washed with distilled water, or the solvent is evaporated to dryness, and if necessary, washed with distilled water and dried to obtain a hydroxyl group. A compound in which a hydrogen atom is substituted with an allyl group.

Thereafter, the allylic group introduced into the phenolic hydroxyl group can be transferred by Cressen recombination by heating.

In the present embodiment, the allyl group is reacted in the presence of a radical or an acid/base, and the solubility in an acid, a base or an organic solvent used in a coating solvent or a developing solution changes. The above-mentioned group substituted with an allyl group is preferably formed to have a property of inducing a chain reaction in the presence of a radical or an acid/base in order to further form a pattern of high sensitivity and high resolution.

 [Resin obtained by using the compound represented by the formula (0) as a monomer]  

The compound represented by the above formula (0) can be used as a composition for forming a film for lithography or a film for forming an optical component (hereinafter, simply referred to as "composition"). Further, a resin obtained by using the compound represented by the above formula (0) as a monomer can be used as a composition. The resin can be obtained, for example, by reacting a compound represented by the above formula (0) with a compound having crosslinking reactivity. Hereinafter, a resin obtained by using the compound represented by the formula (0) as a monomer and a resin obtained by using the compound represented by the formula (1) as a monomer will be exemplified.

The resin obtained by using the compound represented by the above formula (1) as a monomer may, for example, be a structure represented by the following formula (3). In other words, the composition in the present embodiment may be a resin containing a structure represented by the following formula (3).

In the formula (3), L is an alkylene group having 1 to 30 carbon atoms which may have a substituent, an extended aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number of 1 to 30 which may have a substituent. The alkoxy group or a single bond, the above alkylene group, the above-mentioned extended aryl group and the above alkoxy group may have an ether bond, a ketone bond or an ester bond. Further, the alkylene group and the above alkoxy group may be a linear, branched or cyclic group.

R ⁰ , R ¹ , R ² to R ⁵ , m ² and m ³ , m ⁴ and m ⁵ , p ² to p ⁵ , and n are synonymous with the above formula (1). However, m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ^{5 is} an integer of 2 to 8 or 2 to 9 or m ² or m ³ , At least two of m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9.

At least one of R ² to R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms.

 [Resin obtained by using a compound represented by the formula (0-A) as a monomer]  

The compound represented by the above formula (0-A) can be used as a composition for forming a film for lithography or for forming an optical component (hereinafter, simply referred to as "composition"). Further, a resin obtained by using the compound represented by the above formula (0-A) as a monomer can be used as a composition. The resin can be obtained, for example, by reacting a compound represented by the above formula (0-A) with a compound having crosslinking reactivity.

The resin obtained by using the compound represented by the above formula (0-A) as a monomer may, for example, be a structure represented by the following formula (3-A). In other words, the composition in the present embodiment may be a resin containing the structure represented by the following formula (3-A).

In the formula (3-A), L is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and a aryl group having 6 to 30 carbon atoms which may have a substituent. The alkylene group having 1 to 30 carbon atoms or a single bond may have a substituent, and the above alkylene group, the above aryl group and the above alkoxy group may also have an ether bond, a ketone bond or an ester bond, R ^{0 '} It is synonymous with the above R ^{Y '} , R ^{1 '} is an n-valent group or a single bond having a carbon number of 1 to 60, and R ^{2 '} to R ^{5 '} are each independently, and are an alkyl group having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, An amino group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group, and the above alkoxy group may further contain an ether bond, a keto bond or an ester bond, and here, R ^{2 '} to R ⁵ At least one of ^'is an alkenyloxy group having 2 to 30 carbon atoms, and m ^2' and m ^3' are each independently an integer of 0 to 8, and m ^4' and m ^5' are each independently an integer of 0 to 9. However, m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0 at the same time.

 [Method for Producing Resin Made of Compound of Formula (0) as Monomer and Method of Producing Resin by Using Compound of Formula (0-A) as Monomer]  

The resin in the present embodiment is obtained by reacting a compound represented by the above formula (0) and a compound represented by the formula (0-A) with a compound having crosslinking reactivity. In the compound having a cross-linking reactivity, if the compound represented by the above formula (0) and the compound represented by the formula (0-A) are oligomerized or polymerized, the conventional one can be used without particular limitation. By. Specific examples thereof include, but are not limited to, an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, an unsaturated hydrocarbon group-containing compound, and the like. Specially limited.

Specific examples of the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) include, for example, a compound having the formula (0) and a formula (0). The resin of the structure shown by -A) is a resin which is phenol varnished by a condensation reaction with an aldehyde and/or a ketone which is a compound having crosslinking reactivity.

Here, examples of the aldehyde used in the novolacization of the compound represented by the above formula (0) and the compound represented by the above formula (0-A) include formaldehyde, trioxane, trioxane, and benzaldehyde. , acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl An aldehyde, a naphthaldehyde, an anthracene formaldehyde, a phenanthrene formaldehyde, an anthracene formaldehyde, a furfural or the like is not particularly limited. The ketones include the above ketones. Among these, formaldehyde is better. In addition, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and is 0.2 to 5 moles per mole of the compound represented by the above formula (0) and the compound represented by the above formula (0-A). The ear is better, preferably 0.5~2 moles.

An acid catalyst may be used in the condensation reaction of the compound represented by the above formula (0) and the compound represented by the above formula (0-A) with an aldehyde and/or a ketone. The acid catalyst used herein can be appropriately selected and used by a person skilled in the art, and is not particularly limited. As such an acid catalyst, inorganic acids or organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen bromide acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid. , azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonate An organic acid such as acid or naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. The solid acid or the like is not particularly limited as such. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production and ease of handling. Further, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used is appropriately determined depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited, and is 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. It is better. However, in combination with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, biphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, hydrazine The copolymerization reaction of a compound having a non-conjugated double bond such as a olefin, a 5-vinylnorborn-2-ene, an α-monoolefin, a β-olefin, or a limonene does not necessarily need to be an aldehyde.

A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (0) with an aldehyde and/or a ketone. The reaction solvent in the polycondensation can be appropriately selected and used among those skilled in the art, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixture thereof. Solvents, etc. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited, and is preferably 0 to 2000 by mass based on 100 parts by mass of the reaction raw material. The scope of the serving is good. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. In addition, the reaction method can be appropriately selected from the conventional methods, and is not particularly limited, and examples thereof include a compound represented by the above formula (0) and a compound represented by the above formula (0-A), an aldehyde and/or a ketone. And a method of adding the catalyst once, or a method of dropping the compound represented by the above formula (0) and the compound represented by the above formula (0-A) or an aldehyde and/or a ketone in the presence of a catalyst.

After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out by a general method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the general purpose of removing the volatiles by about 1 to 50 mmhg by using the temperature of the reaction vessel to 130 to 230 ° C can be obtained. a phenolic varnished resin.

Here, the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) may be a compound represented by the above formula (0) and the above formula (0-A). The individual polymers of the compounds shown, but may also be copolymers with other phenols. Here, examples of the copolymerizable phenol include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, and resorcinol. Methyl resorcinol, benzenediol, butyl benzenediol, methoxy phenol, methoxy phenol, propyl phenol, benzene trisphenol, thymol, and the like are not particularly limited.

Further, the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyindole, benzofuran, hydroxyindole, decene, biphenyl, biphenol, and trisole. Phenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, monoolefin, limonene, and the like are not particularly limited. Further, the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) may be a compound represented by the above formula (0) and a formula (0-A). a compound having a structure of two or more (for example, a quaternary four-membered) copolymer of the above phenol, a compound represented by the above formula (0), and a structure represented by the formula (0-A) and the above comonomer a copolymer of 2 or more (for example, 2 to 4) copolymer, a compound represented by the above formula (0), and a structure represented by the formula (0-A), and the above phenol and the above comonomer 3 More than or equal to the (for example, 3 to 4 member) copolymer.

The molecular weight of the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is 500 to 30,000. Better, better 750~20000. In addition, from the viewpoint of improving the crosslinking efficiency and suppressing the volatile component during baking, the resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A), the degree of dispersion ( The weight average molecular weight Mw/number average molecular weight Mn) is preferably in the range of 1.2 to 7. Further, the above Mw and Mn can be obtained by the method described in the examples below.

The resin having the structure represented by the above formula (3) and the resin having the structure represented by the formula (3-A) are more soluble in a solvent from the viewpoint of being more easily applied in a wet process or the like. It is better. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility of the solvent is preferably 10% by mass or more. . Here, the solubility of PGME and/or PGMEA is defined as "mass of resin (mass of resin + mass of solvent) × 100 (% by mass)". For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin to PGMEA is "10 mass% or more", and when it is not dissolved, it is "less than 10 mass%".

 [Compound represented by formula (2)]  

The compound represented by the formula (0) in the present embodiment is preferably a compound represented by the following formula (2) from the viewpoint of heat resistance and solvent solubility.

In the formula (2), R ^0A is synonymous with the above R ^Y and a hydrogen atom.

R ^1A is n-1 to 30 carbon atoms of the divalent group ^A or a single bond, R ^2A independently, which may have a substituent group of a carbon number of an alkyl group having 1 to 30, carbon atoms may have a substituent of an aryl group having 6 to 30 of a base having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group. the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may contain an ether bond, ketone or ester linkages, herein, at least one of R ^2A is hydroxy, and at least one R ^2A is a C 2 to 30 alkenyl.

The n ^A system is synonymous with the above N, and is an integer of 1 to 4. Here, in the formula (2), when n ^A is an integer of 2 or more, the structural formulae of n ^A [ ] may be the same or different.

X ^{A is} independent of each other and represents an oxygen atom, a sulfur atom, a single bond or no crosslinking. Here, X ^A tends to have an excellent oxygen resistance, preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom. From the viewpoint of solubility, X ^A is preferably a non-crosslinker.

m ^{2A is} independent of each other and is an integer from 0 to 7. However, at least one m ^2A is an integer of 2 to 7 or at least two of m ^2A is an integer of 1 to 7.

q ^{A is} independent, 0 or 1.

Further, the above-mentioned n-valent group means an alkyl group having 1 to 60 carbon atoms when n=1, an alkylene group having 1 to 30 carbon atoms when n=2, and a carbon number of 2 to 60 when n=3. An alkane propyl group, when n=4, is an alkane tetra group having a carbon number of 3 to 60. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Although the compound represented by the above formula (2) has a relatively low molecular weight, it has high heat resistance due to its straight structure, and can be used under high-temperature baking conditions. Further, since the molecule has a grade 3 carbon or a grade 4 carbon, the crystallinity is suppressed, and a composition for forming a film for lithography used in the production of a film for lithography can be used.

In addition, since the solubility in a safe solvent is high and heat resistance and etching resistance are good, a composition for forming a lithography agent containing the compound represented by the above formula (2) can form a favorable resist pattern shape.

Furthermore, because of the lower molecular weight and low viscosity, even a substrate having a step (especially a fine pitch or a via pattern, etc.) can be easily filled uniformly to the corners of the step and the film is flattened. The results showed that the composition was formed using the underlayer film by lithography, and the embedding and planarization characteristics were good. Further, since it is a compound having a relatively high carbon concentration, high etching resistance can be imparted.

Further, since the aromatic density is high and the refractive index is high, and coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, it can be used as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferred from the viewpoint of suppressing oxidative decomposition of the compound and suppressing coloration, and improving heat resistance and solvent solubility. In terms of optical parts, in addition to film-like and sheet-like parts, it can also be used as a plastic lens (稜鏡 lens, convex lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, A film for electromagnetic wave shielding, germanium, an optical fiber, a solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the above formula (2) is more preferably a compound represented by the following formula (2-1) from the viewpoint of ease of crosslinking and solubility in an organic solvent.

In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^A are synonymous with those described in the above formula (2).

R ^3A is an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, and a nitro group. An amine group, a carboxylic acid group or a thiol group, and in the same naphthalene ring or benzene ring, may be the same or different. Here, at least one of R ^{3A is} an alkenyl group having 2 to 30 carbon atoms, and R ^{4A is} independently a hydrogen atom, and m ^{6A is} independently an integer of 0 to 5.

When a compound represented by the above formula (2-1) is used as a composition for a lithographic film for an alkali-developing positive resist or an organic developing negative resist, at least one of R ^4A is an acid-dissociable group. . On the other hand, when the compound represented by the formula (2-1) is used as a composition for forming a lithography film for an alkali-developing negative resist, and a composition for forming a film for lithography of a lower film or a component for forming an optical component, At least one of R ^4A is a hydrogen atom.

 [Compound represented by formula (2-A)]  

The compound (0-A) in the present embodiment is preferably a compound represented by the following formula (2-A) from the viewpoint of heat resistance and solvent solubility.

(In the formula (2A), R ^{0A 'system} and the above-described R ^Y' is synonymous, R ^{1A 'is} a n 1 ~ 30 carbon atoms of the divalent group ^A or a single bond, R ^2A' each independently may have a substituent An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and an alkyl group having 1 to 30 carbon atoms which may have a substituent An oxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, the above aryl group, the above alkenyl group and the above alkoxy group may further contain an ether bond, a ketone bond or an ester bond. ^'is an integer of 2 or more, n ^a' here, R ^{2A 'is} at least 1 to 30 carbon atoms, alkenyl of 2-yloxy, n ^a' is synonymous with the above-described line N, here, n ^a number of [ The structural formulas within the formula may be the same or different, X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^2A' are each independently an integer of 0-7, but at least one m ^2A' Is an integer from 1 to 7, q ^{A' is} independent, 0 or 1).

Further, the base of the above n' valence means an alkyl group having 1 to 60 carbon atoms when n'=1, an alkylene group having 1 to 30 carbon atoms when n'=2, and a carbon number 2 when n'=3. 60 alkane propyl, n' = 4 is a carbon number of 3 to 60 alkane tetrayl. Examples of the above-mentioned n-valent group include those having a linear hydrocarbon group, a branched hydrocarbon group or an alicyclic hydrocarbon group. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group. Further, the n-valent group may have an aromatic group having 6 to 60 carbon atoms.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 60 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Further, the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms. Here, the above alicyclic hydrocarbon group also contains a bridged aliphatic hydrocarbon group.

Although the compound represented by the above formula (2-A) has a relatively low molecular weight, it can be used under high-temperature baking conditions because of its straight structure and high heat resistance. Further, since the molecule has a grade 3 carbon or a grade 4 carbon, the crystallinity is suppressed, and a composition for forming a film for lithography used in the production of a film for lithography can be used.

Moreover, since the solubility in a safe solvent is high and heat resistance and etching resistance are good, the composition for forming a lithography agent containing the compound represented by the above formula (2-A) can impart a good resist pattern shape.

Furthermore, because of the lower molecular weight and low viscosity, even a substrate having a step (especially a fine pitch or a via pattern, etc.) can be easily filled uniformly to the corners of the step and the film is flattened. The results showed that the composition was formed by the underlayer film using lithography, and the embedding and planarization characteristics were good. Further, since it is a compound having a relatively high carbon concentration, high etching resistance can be imparted.

Further, since the aromatic density is high and the refractive index is high, and coloring is suppressed by heat treatment in a wide range from low temperature to high temperature, it can be used as a composition for forming various optical components. Among them, a compound having a carbon of 4 grade is preferred from the viewpoint of suppressing oxidative decomposition of the compound and suppressing coloration, and improving heat resistance and solvent solubility. In terms of optical parts, in addition to film-like and sheet-like parts, it can also be used as a plastic lens (稜鏡 lens, convex lens, microlens, Fresnel lens, viewing angle control lens, contrast lifting lens, etc.), retardation film, A film for electromagnetic wave shielding, germanium, an optical fiber, a solder resist for a flexible printed wiring, a plating resist, an interlayer insulating film for a multilayer printed wiring board, and a photosensitive optical waveguide.

The compound represented by the above formula (2-A) is more preferably a compound represented by the following formula (2-1-A) from the viewpoint of ease of crosslinking and solubility in an organic solvent.

(In the formula ^{(2-1-A), R 0A} ', R 1A', n A ', q A' and X ^{A 'is} synonymous with the line (2-A) in the formula, R ^3A' each independently, is An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group And a carboxylic acid group or a thiol group, wherein R ^{4A′ is} independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms, and at least one of R ^4A′ is an alkenyl group having 2 to 30 carbon atoms. , m ^6A' are independent, each is an integer from 0 to 5.)

When a compound represented by the above formula (2-1-A) is used as a composition for a lithographic film for an alkali-developing positive resist or an organic developing negative resist, at least one of R ^4A' is an acid. Dissociative group. On the other hand, the compound represented by the formula (2-1-A) is used as a composition for forming a lithography film for an alkali-developing negative resist, a film forming composition for a lithography for a lower film, or an optical component forming composition. At least one of R ^4A' is a hydrogen atom.

Further, the compound represented by the above formula (2-1-A) is more preferably a compound represented by the following formula (2a-A) from the viewpoint of the supply property of the raw material.

In the above formula (2a-A), X ^{A '} , R ^{0A '} to R ^2A' , m ^2A' and n ^{A '} are synonymous with those described in the above formula (2-A).

Further, the compound represented by the above formula (2-1-A) is more preferably a compound represented by the following formula (2b-A) from the viewpoint of solubility in an organic solvent.

In the above formula (2b-A), X ^A' , R ^0A' , R ^1A' , R ^3A' , R ^4A' , m ^6A' and n ^A' are as described in the above formula (2-1-A). Synonymous.

Further, the compound represented by the above formula (2-1-A) is more preferably a compound represented by the following formula (2c-A) from the viewpoint of solubility in an organic solvent.

In the above formula (2c-A), X ^A' , R ^0A' , R ^1A' , R ^3A' , R ^4A' , m ^6A' and n ^A' are as described in the above formula (2-1-A). Synonymous.

The compound represented by the above formula (2-A) has the following formula (BisN-1-A)~(BisN-4-A), (XBiN-1-A) from the viewpoint of further solubility in an organic solvent. The compound shown by ~(XBiN-3-A) is excellent.

 [Method for Producing Compound of Formula (2) and Method for Producing Compound of Formula (2-A)]  

The compound represented by the formula (2) and the compound represented by the formula (2-A) in the present embodiment can be suitably synthesized by a conventional method, and the synthesis method is not particularly limited.

For example, under normal pressure, a polyphenol compound is obtained by polycondensation reaction of a biphenol, a binaphthol or a hydrazine phenol with a corresponding ketone under an acid catalyst, followed by at least one polyphenol compound. The phenolic hydroxyl group is introduced into the allyl group to give a compound represented by the formula (2-A). Thereafter, the compound represented by the formula (2) can be obtained by heating the compound represented by the formula (2-A) to recombine Kreisen. These reactions can be carried out under pressure as needed.

The timing of introducing the allyl group can be introduced after the production of the resin in the pre-stage, the post-stage of the condensation reaction or later.

The naphthols are not particularly limited, and examples thereof include naphthol, methylnaphthol, methoxynaphthol, and naphthalenediol. Among them, from the viewpoint of easily forming a xanthene structure, It is preferred to use naphthalenediol.

The phenol is not particularly limited, and examples thereof include phenol, methyl phenol, methoxybenzene, benzenediol, resorcin, hydroquinone, and trimethylhydroquinone.

Examples of the ketones include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornrone, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzene. Anthrone, anthraquinone, ethane naphthone, anthracene, acetophenone, diethyl benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, Diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoneone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. It is not particularly limited by these. These may be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, cyclopentanone, cyclohexanone, norbornone, tricyclohexanone, tricyclic fluorenone, adamantanone, anthrone, benzopyrene are used. Ketone, anthraquinone, ethane naphthone, anthracene, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl a carbonyl biphenyl, a benzophenone, a diphenylcarbonylbenzene, a triphenylcarbonylbenzene, a benzonaphthone, a diphenylcarbonylnaphthalene, a phenylcarbonylbiphenyl group, a diphenylcarbonylbiphenyl group, preferably. From the standpoint of improving etching resistance, acetophenone, diethyl benzene benzene, triethylene phenyl benzene, naphthyl ethyl ketone, diphenyl carbonyl naphthalene, phenyl carbonyl biphenyl, diphenyl carbonyl is used. Phenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzoneone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl are more preferred.

In terms of ketones, it is preferred to use a ketone having an aromatic ring from the viewpoint of having both high heat resistance and high etching resistance.

The acid catalyst used in the above reaction can be appropriately selected and used from a conventional one, and is not particularly limited. The acid catalyst may be appropriately selected from conventional inorganic acids and organic acids, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen bromide acid, and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, and methane; Organic acids such as sulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid; Lewis, zinc chloride, aluminum chloride, ferric chloride, boron trifluoride, etc. Acid; or a solid acid such as tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. Among these, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of ease of manufacture or ease of handling. The acid catalyst may be used singly or in combination of two or more.

In the case of the above reaction, a reaction solvent can also be used. The reaction solvent is not particularly limited as long as it can be reacted with a ketone or naphthol used, and for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or These mixed solvents. The amount of the reaction solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass based on 100 parts by mass of the reaction raw material.

The reaction temperature is not particularly limited and may be appropriately selected depending on the reactivity of the reaction raw material, but it is preferably in the range of 10 to 200 °C. From the viewpoint of selectively synthesizing the compound represented by the formula (2) in the present embodiment, the temperature is preferably lower, and the range of 10 to 60 ° C is more preferable.

The reaction method is not particularly limited, and examples thereof include a method of adding a naphthol or the like, an aldehyde or a ketone, a catalyst, or a method of dropping a naphthol or an aldehyde or a ketone in the presence of a catalyst. In order to remove unreacted raw materials, catalysts, and the like which are present in the system after completion of the polycondensation reaction, the volatile matter can be removed by raising the temperature of the reaction vessel to 130 to 230 ° C and at about 1 to 50 mmHg.

The amount of the raw material is not particularly limited. For example, with respect to the ketone 1 mole, 2 moles to excess amount such as naphthol and 0.001 to 1 mole of acid catalyst can be used, and 20 to 60 at normal pressure. It is preferable to carry out the reaction for 20 minutes to 100 hours at °C.

After the reaction is completed, the object can be isolated by a conventional method. The method of arranging the target product is not particularly limited, and for example, the reaction solution is concentrated, and the reaction product is precipitated by adding pure water. After cooling to room temperature, the mixture is filtered and separated, and the obtained solid matter is filtered and dried. A method in which a target compound is obtained by column chromatography, separation and purification from a by-product, and distillation of a solvent, filtration, and drying.

Further, a method of introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.

For example, as described below, an allyl group can be introduced into at least one phenolic hydroxyl group of the above compound.

The compound for introducing an allyl group can be synthesized or easily obtained by a conventional method, and examples thereof include allyl chloride, allyl bromide, and allyl iodide, but these are not particularly limited. .

First, the above compound is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF) or propylene glycol monomethyl ether acetate. Next, it is allowed to react at normal pressure and at 20 to 150 ° C for 6 to 72 hours in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide or sodium ethoxide. The reaction solution is neutralized with an acid, added to distilled water to precipitate a white solid, and the separated solid is washed with distilled water, or the solvent is evaporated to dryness, and if necessary, washed with distilled water and dried to obtain a hydroxyl group. A compound in which a hydrogen atom is substituted with an allyl group.

In the present embodiment, the allyl group is reacted in the presence of a radical or an acid/base, and the solubility in an acid, a base or an organic solvent used in a coating solvent or a developing solution changes. The above-mentioned group substituted with an allyl group is preferably one which has a property of initiating a chain reaction in the presence of a radical or an acid/base in order to further form a pattern of high sensitivity and high resolution.

Thereafter, the allylic group introduced into the phenolic hydroxyl group can be transferred by Cressen recombination by heating.

 [Resin obtained by using the compound represented by the formula (2) as a monomer]  

The compound represented by the above formula (2) can be used as a composition for forming a film for lithography or a composition for forming an optical component. Further, a resin obtained by using the compound represented by the above formula (2) as a monomer can be used as a composition. The resin can be obtained, for example, by reacting a compound represented by the above formula (2) with a compound having crosslinking reactivity.

The resin obtained by using the compound represented by the above formula (2) as a monomer may, for example, be a structure represented by the following formula (4). In other words, the composition in the present embodiment may contain a resin having a structure represented by the following formula (4).

In the formula (4), L is a linear or branched alkyl or single bond having 1 to 30 carbon atoms.

R ^0A , R ^1A , R ^2A , m ^2A , n ^A , q ^A and X ^A are synonymous with the above formula (2), but when n ^A is an integer of 2 or more, n ^A of [ ] structure formula may be the same or different, at least one of m ^2A is an integer of 2 to 6, or at least two of the m ^2A is an integer of 1 to 6, R ^2A is hydroxy, at least 1, and at least one of R ^2A It is an alkenyl group having 2 to 30 carbon atoms.

 [Resin obtained by using the compound represented by the formula (2-A) as a monomer]  

The compound represented by the above formula (2-A) can be used as it is as a composition for forming a film for lithography or a composition for forming an optical component. Further, a resin obtained by using the compound represented by the above formula (2-A) as a monomer can be used as a composition. The resin can be obtained, for example, by reacting a compound represented by the above formula (2-A) with a compound having crosslinking reactivity.

The resin obtained by using the compound represented by the above formula (2-A) as a monomer may, for example, be a structure represented by the following formula (4-A). In other words, the composition in the present embodiment may be a resin containing a structure represented by the following formula (4-A).

(In the formula (4-A), L' is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^{0A '} is synonymous with the above R ^{Y '} , and R ^1A' is a carbon number. 1 to 30 of the n-valent group ^a or a single bond, R ^{2A 'independently,} which may have an alkyl group having a carbon number of 1 to 30 substituted, the substituent group may have a carbon number of the aryl group having 6 to 30, may have a The alkenyl group having 2 to 30 carbon atoms of the substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the above alkyl group, The aryl group, the alkenyl group and the alkoxy group may further contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^{2A' is} an alkenyloxy group having 2 to 30 carbon atoms, and the n ^{A '} is a Synonymous with the above N, where n ^{A '} is an integer of 2 or more, the structural formulas in [ ] of n ^{A '} may be the same or different, and X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no cross. In addition, m ^{2A' is} independent, and is an integer of 0 to 7, except that at least one m ^2A' is an integer of 1 to 7, and q ^{A' is} independent of 0 or 1).

 [Method for producing a resin obtained by using the compound represented by the formula (2) as a monomer and a method for producing a resin obtained by using the compound represented by the formula (2-A) as a monomer]  

The resin in the present embodiment is obtained by reacting a compound represented by the above formula (2) and a compound represented by the formula (2-A) with a compound having crosslinking reactivity. In the case of the compound having the crosslinking reactivity, the compound represented by the above formula (2) and the compound represented by the formula (2-A) may be oligomerized or polymerized, and may be, without particular limitation. Use the learner. Specific examples thereof include, but are not limited to, an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amine compound, an imine compound, an isocyanate, an unsaturated hydrocarbon group-containing compound, and the like. Specially limited.

Specific examples of the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) include, for example, the compound represented by the above formula (2) and the formula (2-A). The compound shown is a resin which is novolak-treated by a condensation reaction with an aldehyde and/or a ketone which is a compound having crosslinking reactivity.

Here, examples of the aldehyde used in the case where the compound represented by the above formula (2) and the compound represented by the formula (2-A) are subjected to novolak-forming are, for example, formaldehyde, trioxane, trioxane, benzaldehyde, Acetaldehyde, propyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methyl benzaldehyde, ethyl benzaldehyde, butyl benzaldehyde, biphenyl aldehyde , naphthacene, hydrazine formaldehyde, phenanthrene formaldehyde, hydrazine formaldehyde, furfural, etc., but are not particularly limited thereto. Examples of the ketone include the above ketones. Among these, formaldehyde is preferred. In addition, these aldehydes and/or ketones may be used alone or in combination of two or more. Further, the amount of the aldehyde and/or ketone used is not particularly limited, and is 0.2 to 5 moles per mole of the compound represented by the above formula (2) and the compound 1 represented by the formula (2-A). Better, better 0.5~2 moles.

An acid catalyst may be used in the condensation reaction of the compound represented by the above formula (2) and the compound represented by the formula (2-A) with an aldehyde and/or a ketone. The acid catalyst used herein can be appropriately selected and used by a person skilled in the art, and is not particularly limited. As such an acid catalyst, inorganic acids or organic acids are widely known, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen bromide acid, and hydrofluoric acid; oxalic acid, malonic acid, succinic acid, and adipic acid. , azelaic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonate An organic acid such as acid or naphthalene disulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, iron chloride or boron trifluoride; or tungstic acid, phosphotungstic acid, lanthanum molybdate or phosphomolybdic acid. A solid acid or the like is not particularly limited as such. Among these, an organic acid or a solid acid is preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of ease of production and ease of handling. Further, the acid catalyst may be used singly or in combination of two or more.

In addition, the amount of the acid catalyst to be used is appropriately determined depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited. It is preferably 0.01 to 100 parts by mass based on 100 parts by mass of the reaction raw material. . However, in combination with hydrazine, hydroxy hydrazine, benzofuran, hydroxy hydrazine, decene, biphenyl, biphenol, trisphenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, hydrazine The copolymerization reaction of a compound having a non-conjugated double bond such as a olefin, a 5-vinylnorborn-2-ene, an α-monoolefin, a β-olefin, or a limonene does not necessarily need to be an aldehyde.

A reaction solvent can be used for the condensation reaction of the compound represented by the above formula (2) and the compound represented by the formula (2-A) with a ketone. The reaction solvent in the polycondensation can be appropriately selected and used among those skilled in the art, and is not particularly limited, and examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane or a mixture thereof. Solvents, etc. Further, the solvent may be used alone or in combination of two or more.

In addition, the amount of the solvent to be used may be appropriately set depending on the type of the catalyst to be used and the type of the catalyst to be used, and is not particularly limited, and is preferably 0 to 2000 by mass based on 100 parts by mass of the reaction raw material. The scope of the serving is good. Further, the reaction temperature is appropriately selected depending on the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 °C. In addition, the reaction method can be appropriately selected from the conventional methods, and is not particularly limited, and examples thereof include a compound represented by the above formula (2) and a compound represented by the formula (2-A), an aldehyde and/or a ketone, A method of adding a catalyst once, or a method of dropping a compound represented by the above formula (2) and a compound represented by the formula (2-A) or an aldehyde and/or a ketone in the presence of a catalyst.

After completion of the polycondensation reaction, the isolation of the obtained compound can be carried out by a general method, and is not particularly limited. For example, in order to remove unreacted raw materials or catalysts present in the system, the general purpose of removing the volatiles by using the temperature of the reaction vessel to 130 to 230 ° C and removing the volatiles by about 1 to 50 mmHg is obtained. a phenolic varnished resin.

Here, the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) may be a compound represented by the above formula (2) and a formula (2-A). The individual polymers of the compounds shown, but may also be copolymers with other phenols. Here, examples of the copolymerizable phenol include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, and resorcinol. Methyl resorcinol, benzenediol, butyl benzene, methoxy phenol, methoxy phenol, propyl phenol, benzene trisphenol, thymol, etc., but are not particularly limited thereto.

Further, the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) may be copolymerized with a polymerizable monomer in addition to the above other phenols. Examples of the comonomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, anthracene, hydroxyindole, benzofuran, hydroxyindole, decene, biphenyl, biphenol, and trisole. Phenol, dicyclopentadiene, tetrahydroanthracene, 4-vinylcyclohexene, norbornadiene, vinyl norbornene, monoolefin, limonene, etc., but are not particularly limited thereto. Further, the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) may be a compound represented by the above formula (2) and a compound represented by the formula (2). Two or more (for example, two to four-membered) copolymers of the above phenols, a compound represented by the above formula (2), and a compound represented by the formula (2) and two or more of the above-mentioned comonomers (for example, a 2 to 4 member copolymer, a compound represented by the above formula (2), a compound represented by the formula (2), and a ternary or higher ternary member of the phenol and the comonomer (for example, a 3-4 member) Copolymer.

Further, the molecular weight of the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) is not particularly limited, and the weight average molecular weight (Mw) in terms of polystyrene is 500. ~30000 is better, more preferably 750~20000. In addition, from the viewpoint of improving the crosslinking efficiency and suppressing the volatile component during baking, the resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) are dispersed. The degree (weight average molecular weight Mw / number average molecular weight Mn) is preferably in the range of 1.2 to 7. Further, the above Mw and Mn can be obtained by the method described in the examples below.

The resin having the structure represented by the above formula (4) and the resin having the structure represented by the formula (4-A) are more soluble in a solvent, from the viewpoint of being more easily applied in a wet process, and the like. It is better. More specifically, when 1-methoxy-2-propanol (PGME) and/or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility of the solvent is preferably 10% by mass or more. . Here, the solubility of PGME and/or PGMEA is defined as "mass of resin (mass of resin + mass of solvent) × 100 (% by mass)". For example, when 10 g of the above resin is dissolved in 90 g of PGMEA, the solubility of the resin to PGMEA is "10 mass% or more", and when it is not dissolved, it is "less than 10 mass%".

 [Purification method of compound and / or resin]  

The method for purifying a compound and/or a resin in the present embodiment includes a step of obtaining a resin obtained by selecting a compound represented by the above formula (0) and a compound represented by the above formula (0) as a monomer. The compound represented by the above formula (0-A) and the resin obtained by using the compound represented by the above formula (0-A) as a monomer, more specifically, selected from the above formula (1) a compound obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), and a resin obtained by using the compound represented by the above formula (2) as a monomer, and the above formula ( a compound represented by 1-A), a resin obtained by using the compound represented by the above formula (1-A) as a monomer, a compound represented by the above formula (2-A), and the above formula (2-A) The step of dissolving one or more kinds of the resin obtained as a monomer in a solvent to obtain a solution (S), contacting the obtained solution (S) with an acidic aqueous solution, and extracting impurities in the above compound and/or the above resin (first extraction step), wherein the solvent used in the step of obtaining the above solution (S) comprises a solvent which is not optionally mixed with water

In the first extraction step, the resin is a compound represented by the above formula (1) and/or a compound represented by the formula (2) and a compound represented by the formula (1-A) and/or a formula (2). A resin obtained by reacting a compound represented by -A) with a compound having crosslinking reactivity is preferred. According to the purification method of the present embodiment, the content of various metals contained as impurities in the compound or resin having a specific structure can be reduced.

More specifically, in the purification method of the present embodiment, the compound and/or the resin is dissolved in an organic solvent which is not arbitrarily mixed with water to obtain a solution (S), and the solution (S) is brought into contact with an acidic aqueous solution. To carry out the extraction treatment. Thereby, the metal component contained in the above solution (S) can be transferred to the aqueous phase, and then the organic phase and the aqueous phase can be separated to obtain a compound and/or a resin having a reduced metal content.

The compound and/or the resin used in the purification method of the present embodiment may be used singly or in combination of two or more. Further, the above compound or resin may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers, and the like.

The solvent to be used in the purification method of the present embodiment which is not arbitrarily mixed with water is not particularly limited, and is preferably an organic solvent which can be safely applied to a semiconductor manufacturing process, and specifically, it can be used at room temperature. The solubility of water is less than 30%, more preferably less than 20%, and even more preferably less than 10% organic solvent. The amount of the organic solvent to be used is preferably from 1 to 100 times by mass based on the total amount of the compound to be used and the resin.

Specific examples of the solvent which is not optionally mixed with water are not limited thereto, and examples thereof include ethers such as diethyl ether and diisopropyl ether; ethyl acetate, n-butyl acetate, and acetic acid. a ketone such as an ester of isoamyl or the like, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone or 2-pentanone; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate An aliphatic hydrocarbon such as n-hexane or n-heptane; an aromatic hydrocarbon such as toluene or xylene; or a halogenated hydrocarbon such as dichloromethane or chloroform. Among them, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate is preferred, methyl isobutyl ketone Further, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate is more preferable, and methyl isobutyl ketone and ethyl acetate are more preferable. Methyl isobutyl ketone, ethyl acetate, etc., because the resin containing the above compound and the compound as a constituent component has a high saturated solubility and a low boiling point, and can be removed by industrial distillation or by drying. The load of the steps. These solvents may be used singly or in combination of two or more.

The acidic aqueous solution used in the purification method of the present embodiment can be appropriately selected from aqueous solutions obtained by dissolving a conventionally known organic compound or inorganic compound in water. The acidic aqueous solution is not limited thereto, and examples thereof include a mineral acid aqueous solution obtained by dissolving a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid in water; and acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid. An aqueous solution of an organic acid in which an organic acid such as fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid or trifluoroacetic acid is dissolved in water. These acidic aqueous solutions may be used singly or in combination of two or more. Among these acidic aqueous solutions, one or more kinds of mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, An aqueous solution of one or more organic acids selected from the group consisting of maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid is preferred, and sulfuric acid, nitric acid, and acetic acid are used. An aqueous solution of a carboxylic acid such as oxalic acid, tartaric acid or citric acid is more preferable, and an aqueous solution of sulfuric acid, oxalic acid, tartaric acid, and citric acid is more preferable, and an aqueous solution of oxalic acid is more preferable. A polyvalent carboxylic acid such as oxalic acid, tartaric acid or citric acid has a chelate effect by coordinating with a metal ion, and therefore it is considered that there is a tendency to remove the metal more effectively. Further, the water to be used herein preferably uses water having a small metal content such as ion-exchanged water or the like in accordance with the purpose of the purification method of the present embodiment.

In the purification method of the present embodiment, the pH of the acidic aqueous solution to be used is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the above compound or resin. The pH of the acidic aqueous solution is usually about 0 to 5, preferably about pH 0 to 3.

In the purification method of the present embodiment, the amount of the acidic aqueous solution to be used is not particularly limited, but the use is adjusted from the viewpoint of reducing the number of extractions for removing metals and the amount of liquid to ensure the operability. The amount is better. From the above viewpoints, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass based on 100% by mass of the solution (S).

In the purification method of the present embodiment, the acidic component is brought into contact with the solution (S) to extract the metal component from the compound or the resin in the solution (S).

In the purification method of the present embodiment, the solution (S) is preferably an organic solvent which is optionally mixed with water. When the solution (S) contains an organic solvent arbitrarily mixed with water, the amount of the compound and/or the resin to be added may be increased, and the liquid separation property may be improved, and the purification may be performed with high efficiency. The method of adding an organic solvent arbitrarily mixed with water is not particularly limited, and examples thereof include a method of previously adding a solution containing an organic solvent, a method of previously adding to water or an acidic aqueous solution, and a solution containing an organic solvent with water or an acidic aqueous solution. Any of the methods added after contact. Among these, a method of adding a solution containing an organic solvent in advance is preferable from the viewpoint of workability of operation or easy management of the amount of addition.

The organic solvent to be arbitrarily mixed with water used in the purification method of the present embodiment is not particularly limited, and an organic solvent which can be safely applied in a semiconductor manufacturing process is preferred. The range in which the amount of the organic solvent to be arbitrarily mixed with water is such that the solution phase and the aqueous phase are separated is not particularly limited, and is preferably 0.1 to 100 mass times, and 0.1 to 50 mass, based on the total amount of the compound and the resin to be used. More preferably, 0.1 to 20 times better.

Specific examples of the organic solvent optionally mixed with water used in the purification method of the present embodiment are not limited, and examples thereof include ethers such as tetrahydrofuran and 1,3-dioxolane; and methanol and ethanol. Alcohols such as isopropyl alcohol; ketones such as acetone and N-methylpyrrolidone; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl An aliphatic hydrocarbon such as a glycol ether such as ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are more preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable. These solvents may be used alone or in combination of two or more.

The temperature at the time of the extraction treatment is usually in the range of 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation can be carried out, for example, by thoroughly mixing after stirring or the like, followed by standing. Thereby, the metal component contained in the solution (S) migrates to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and deterioration of the compound and/or the resin can be suppressed.

The mixed solution is separated into a solution phase containing a compound and/or a resin and a solvent and an aqueous phase by standing, and the solution phase is recovered by decantation or the like. Although the time for standing is not particularly limited, it is preferable to adjust the time of standing by the viewpoint of better separation of the solvent-containing solution phase from the aqueous phase. Usually, the standing time is 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more. Further, it is also possible to carry out the extraction treatment only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.

In the purification method of the present embodiment, the step of extracting the impurity in the compound or the resin by contacting the solution phase containing the compound or the resin with water after the first extraction step (second extraction step) It is better. Specifically, for example, after the extraction treatment is carried out using an acidic aqueous solution, the solution containing the compound and/or the resin and the solvent extracted from the aqueous solution is further supplied to the extraction treatment with water. The extraction treatment with water is not particularly limited, and for example, the solution solution can be sufficiently mixed by stirring with water or the like, and then the obtained mixed solution can be allowed to stand. Since the mixed solution after standing is separated into a solution phase containing a compound and/or a resin and a solvent, the solution phase can be recovered by decantation or the like.

Further, the water used herein is preferably water having a small metal content such as ion-exchanged water or the like according to the purpose of the embodiment. It does not matter if the extraction treatment is performed once, but it is also effective to repeat the mixing, standing, and separation operations. Further, the use ratio of the two of the extraction treatments, the conditions such as the temperature and the time are not particularly limited, and may be the same as the previous treatment with an acidic aqueous solution.

The water which can be mixed in the solution containing the compound and/or the resin and the solvent thus obtained can be easily removed by an operation such as distillation under reduced pressure. Further, a solvent may be added to the above solution as necessary to adjust the concentration of the compound and/or the resin to an arbitrary concentration.

The method for separating the compound and/or the resin from the obtained solution containing the compound and/or the resin and the solvent is not particularly limited, and may be carried out by a conventional method such as removal under reduced pressure, separation by reprecipitation, and a combination thereof. . A conventional treatment such as a concentration operation, a filtration operation, a centrifugal separation operation, a drying operation, and the like can be performed as necessary.

 [composition]  

The lithographic film forming composition of the present embodiment contains a compound represented by the above formula (0), a resin obtained by using the compound represented by the above formula (0) as a monomer, and the above formula (0-A). The compound obtained by using the compound represented by the above formula (0-A) as a monomer, more specifically, the compound represented by the above formula (1), and the compound represented by the above formula (1) The resin obtained as a monomer, the compound represented by the above formula (2), and the resin obtained by using the compound represented by the above formula (2) as a monomer, and the compound represented by the above formula (1-A), The resin represented by the formula (1-A) is obtained by using a resin obtained as a monomer, a compound represented by the above formula (2-A), and a resin obtained by using the compound represented by the above formula (2-A) as a monomer. One or more selected from the group.

The composition of the present embodiment can be a film forming composition or an optical component forming composition for lithography.

 [Chemical Amplifying Resist Application Orientation for Membrane Forming Composition]  

The film formation composition for lithography (hereinafter referred to as "resist composition") for the chemical amplification type resist application orientation in the present embodiment contains the compound represented by the above formula (0), and the above formula (0) The resin obtained as a monomer, the compound represented by the above formula (0-A), and the resin obtained by using the compound represented by the above formula (0-A) as a monomer, more specifically, the above a compound represented by the formula (1), a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), and a compound represented by the above formula (2) as a monomer The obtained resin, the compound represented by the above formula (1-A), the resin obtained by using the compound represented by the above formula (1-A) as a monomer, the compound represented by the above formula (2-A), and the above formula One or more selected from the group formed by (2-A) are used as a resist substrate.

Further, the composition (resist composition) in the present embodiment is preferably a solvent. The solvent is not particularly limited, and examples thereof include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol. An ethylene glycol monoalkyl ether acetate such as an alcohol mono-n-butyl ether acetate; an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Ethyl acetates; propylene glycol monomethyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate Esters, lactate such as n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, C An aliphatic carboxylic acid ester of acid methyl ester, ethyl propionate or the like; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionic acid ethyl ester, 3-methoxy-2-methylpropionic acid Methyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionic acid butyl ester, 3-methyl Other esters such as oxy-3-methylbutyric acid butyl ester, acetamethylene acetate methyl ester, pyruvic acid methyl ester, pyruvic acid ethyl group, etc.; aromatic hydrocarbons such as toluene and xylene; 2-heptanone a ketone of 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN), etc.; N,N-dimethylformamide, N-methylacetamide, N, A lactone such as N-dimethylacetamide or N-methylpyrrolidone; a lactone such as γ-lactone; and the like, but it is not particularly limited. These solvents.

The solvent used in the present embodiment is preferably a safe solvent, more preferably selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, methylphenyl ether, butyl acetate, ethyl propionate, and lactic acid. At least one of the ethyl esters is more preferably at least one of PGMEA, PGME and CHN.

In the present embodiment, the amount of the solid component and the amount of the solvent are not particularly limited, and the amount of the solid component and the total mass of the solvent are 100% by mass, preferably 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent. More preferably, the solid content is 1 to 50% by mass and the solvent is 50 to 99% by mass, more preferably 2 to 40% by mass of the solid component, and 60 to 98% by mass of the solvent, particularly preferably 2 to 10% by mass of the solid component and the solvent. 90 to 98% by mass.

The composition (resist composition) of the present embodiment may further contain an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), and other components (F) in terms of other solid components. At least one selected from the group. Further, the term "solid component" as used herein means a component other than a solvent.

Here, the acid generator (C), the crosslinking agent (G), the acid diffusion controlling agent (E), and other components (F) can be used without any particular limitation, for example, International Publication No. 2013 The one described in /024778 is preferred.

 [ blending ratio of each component]  

In the resist composition of the present embodiment, the content of the compound and/or the resin used as the resist substrate is not particularly limited, and is the total mass of the solid component (including the resist base material, the acid generator (C), The total solid content of the component used for any of the crosslinking agent (G), the acid diffusion controlling agent (E), and the other component (F) is the same as the above, and preferably 50 to 99.4% by mass, more preferably 55~. 90% by mass, more preferably 60 to 80% by mass, particularly preferably 60 to 70% by mass. When the content of the compound and/or the resin used as the resist substrate is in the above range, the resolution is further improved and the line edge roughness (LER) tends to be smaller.

Further, when both the compound as the resist substrate and the resin are contained, the above content is the total amount of the two components.

 [Other ingredients (F)]  

In the resist composition of the present embodiment, the resist base material, the acid generator (C), the crosslinking agent (G), and the acid diffusion controlling agent (E) are necessary as long as they do not inhibit the object of the present invention. In addition to the components, a dissolution promoter, a dissolution controlling agent, a sensitizer, a surfactant, an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof, a heat and/or photohardening catalyst, a polymerization inhibitor may be added. , flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, lubricant, antifoaming agent, leveling agent, ultraviolet absorber, surfactant, colorant One or two or more kinds of various additives such as a nonionic surfactant. Further, in the present specification, the other component (F) is referred to as an optional component (F).

In the resist composition of the present embodiment, a resist substrate (hereinafter referred to as "component (A)"), an acid generator (C), a crosslinking agent (G), an acid diffusion controlling agent (E), and an optional component (F) content (ingredient (A) / acid generator (C) / cross-linking agent (G) / acid diffusion controlling agent (E) / optional component (F)), based on the mass % of the solids, Good is 50~99.4/0.001~49/0.5~49/0.001~49/0~49, more preferably 55~90/1~40/0.5~40/0.01~10/0~5, and even better 60 ~80/3~30/1~30/0.01~5/0~1, especially good 60~70/10~25/2~20/0.01~3/0.

The blending ratio of each component is selected from each range so that the total of the components is 100% by mass. When the blending ratio of each component is in the above range, the properties such as sensitivity, resolution, and developability tend to be excellent.

In the resist composition of the present embodiment, the components are usually dissolved in a solvent to form a homogeneous solution, and then, if necessary, it is prepared by, for example, filtration using a filter having a pore diameter of about 0.2 μm.

The resist composition of the present embodiment may contain a compound other than the compound of the present embodiment or a resin, without departing from the object of the present invention. The other resin is not particularly limited, and examples thereof include novolac resin, polyvinyl phenol, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinyl phenol. a polymer of a unit or such a derivative or the like. The content of the other resin is not particularly limited, and may be appropriately adjusted depending on the type of the component (A) to be used. However, it is preferably 30 parts by mass or less, more preferably 10 parts by mass based on 100 parts by mass of the component (A). It is preferably 5 parts by mass or less, and particularly preferably 0 parts by mass, in parts by mass or less.

 [Physical properties of the resist composition, etc.]  

Using the resist composition of the present embodiment, an amorphous film can be formed by spin coating. Further, the resist composition of the present embodiment can be applied to a general semiconductor manufacturing process. By using the compound represented by the above formula (1) and/or formula (2), the type of the resin obtained as a monomer, and/or the type of developing liquid used, a positive resist pattern can be produced and Any of the negative resist patterns.

In the case of a positive resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C. Preferably, 0.05~5Å/sec is better, and 0.0005~5Å/sec is better. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and can be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. It is presumed that the solubility of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent component before and after exposure is dissolved in the exposed portion of the developing solution and insoluble in the developing solution. The contrast of the interface of the unexposed part becomes larger. And there is the effect of lowering the LER and reducing the defect.

In the case of a negative resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of 10 Å/sec or more for the developing solution at 23 ° C. . When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution and is suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution is improved. It is presumed that the minute surface portion of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component dissolves and lowers the LER. There is also the effect of reducing the defect.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ° C for a predetermined period of time, and measuring the film thickness before and after the immersion by a known method such as a visual, ellipsometer or QCM method. .

In the case of a positive resist pattern, the amorphous film formed by spin coating of the resist composition of the present embodiment is subjected to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The portion to be exposed preferably has a dissolution rate of 10 Å/sec or more for the developing solution at 23 ° C. When the dissolution rate is above 10 Å/sec, it is easily soluble in the developing solution and is more suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution is improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the minute surface portion of the resin containing the compound as a constituent component are dissolved and the LER is lowered. There is also a defect reduction effect.

In the case of a negative resist pattern, an amorphous film formed by spin-coating the resist composition of the present embodiment is subjected to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The dissolution rate of the developing solution at 23 ° C in the exposed portion is preferably 5 Å/sec or less, more preferably 0.05 to 5 Å/sec, and more preferably 0.0005 to 5 Å/sec. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and tends to be a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. It is presumed that the solubility of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent component before and after exposure causes undissolved portions and undissolved in the developing solution. The interface contrast of the exposure portion of the developing liquid becomes large. There is also the effect of lowering the LER and reducing the defect.

 [Formation composition for lithography film for non-chemically amplified resist use orientation]  

The component (A) contained in the film forming composition for lithography (hereinafter also referred to as a radiation sensitive composition) for the non-chemically amplified resist use orientation of the present embodiment is a photoactive compound of the diazonaphthoquinone photoactive compound described later. (B) Combined use, g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, can be used as a positive resistance of a compound soluble in a developing solution. Substrate for the agent. The g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray, the properties of the component (A) do not change much, but are insoluble in imaging. The liquid diazonaphthylquinone photoactive compound (B) is changed to a readily soluble compound, and a resist pattern can be produced by a developing step.

The (A) contained in the radiation sensitive composition of the present embodiment is a compound having a relatively low molecular weight, and the roughness of the obtained resist pattern is also extremely small. Further, in the above formula (1), at least one selected from the group consisting of R ⁰ to R ⁵ is preferably an iodine-containing group, and in the above formula (2), R ^0A , R ^1A and R ^2A are used. It is preferred that at least one selected group is a group containing an iodine atom. When the component (A) having a group containing an iodine atom is used as the radiation-sensitive composition of the present embodiment, the absorption energy of radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays is increased, and as a result, the sensitivity is increased. Preferably.

The glass transition temperature of the component (A) contained in the radiation sensitive composition of the present embodiment is preferably 100 ° C or higher, more preferably 120 ° C or higher, still more preferably 140 ° C or higher, and particularly preferably 150 ° C or higher. The upper limit of the glass transition temperature of the component (A) is not particularly limited and is, for example, 400 °C. When the glass transition temperature of the component (A) is within the above range, the semiconductor lithography process tends to maintain the heat resistance of the pattern shape and has a high resolution and the like.

The glass transition temperature of the component (A) contained in the radiation sensitive composition of the present embodiment is preferably less than 20 J/g as determined by differential scanning calorimetry. Further, (crystallization temperature) - (glass transition temperature) is preferably 70 ° C or higher, more preferably 80 ° C or higher, still more preferably 100 ° C or higher, and particularly preferably 130 ° C or higher. When the crystallization heat generation amount is less than 20 J/g or (crystallization temperature)-(glass transition temperature) is within the above range, the amorphous film is easily formed by spin coating the radiation sensitive composition. Moreover, the film forming property necessary for the resist can be maintained for a long period of time, and there is a tendency to improve the resolution.

In the present embodiment, the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be determined by differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu Corporation. About 10 mg of the sample was placed in an unsealed container made of aluminum, and the temperature was raised to a temperature higher than the melting point by a heating rate of 20 ° C /min in a nitrogen gas stream (50 mL / min). After rapid cooling, the temperature was raised to a temperature higher than the melting point by a temperature increase rate of 20 ° C / min in a nitrogen gas stream (30 mL / min). After further rapid cooling, the temperature was again raised to 400 ° C in a nitrogen gas stream (30 mL / min) at a temperature increase rate of 20 ° C / min. The temperature at which the midpoint of the baseline height (the specific heat change is half) is the glass transition temperature (Tg), and the temperature of the heat generation peak which appears later is the crystallization temperature. The calorific value was determined from the area of the region surrounded by the heat peak and the baseline as the crystallization calorific value.

The component (A) contained in the radiation sensitive composition of the present embodiment is preferably 100 or less, preferably 120 ° C or less, more preferably 130 ° C or less, and still more preferably 140 ° C or less, under normal pressure. Below 150 ° C, sublimation is preferred. The low sublimation property means that the weight loss at a predetermined temperature for 10 minutes in the thermogravimetric analysis is 10% or less, preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less. It is 0.1% or less. Because of its low sublimation, it can prevent contamination of the exposure device caused by exhaust gas during exposure. A low roughness and a good pattern shape can be obtained.

The component (A) contained in the radiation sensitive composition of the present embodiment is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), and a ring. Among the solvents which have the highest solubility of the component (A), pentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate are preferred at 23 ° C. 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and particularly preferably a solvent selected from PGMEA, PGME, and CHN and exhibiting the highest solubility in the (A) resist substrate. It is 20% by mass or more in 23 ° C, and it is particularly preferable to dissolve PGMEA at 20 ° C or more at 23 ° C. By conforming to the above conditions, it is possible to use the semiconductor manufacturing steps in actual production.

 [Diazonaphthylquinone photoactive compound (B)]  

The diazonaphthoquinone photoactive compound (B) contained in the radiation sensitive composition of the present embodiment is a diazonaphthoquinone substance containing a polymerizable or non-polymeric diazonaphthoquinone photoactive compound, generally in the positive form. The resist composition is not particularly limited as long as it can be used as a photosensitive component (photosensitive agent), and one type or two or more types can be used arbitrarily.

In the aspect of the component (B), a naphthoquinonediazidesulfonic acid chloride or a benzofluoride diazidosulfonic acid chloride or the like, and a low molecular compound having a functional group capable of condensation reaction with the acid chloride The compound obtained by the reaction of the polymer compound is preferred. Here, the functional group which can be condensed with the acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amine group, and particularly preferably a hydroxyl group. The compound having a hydroxyl group which is condensable with an acid chloride is not particularly limited, and examples thereof include hydroquinone, resorcin, 2,4-dihydroxybenzophenone, and 2,3,4-trihydroxydiphenyl. Methyl ketone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2' , 4,4'-tetrahydroxybenzophenone, 2,2',3,4,6'-pentahydroxybenzophenone, etc., hydroxybenzophenone, bis(2,4-dihydroxyphenyl) a hydroxyphenyl alkane such as methane, bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxyphenyl)propane, 4,4',3",4"-four Hydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',2",3",4"-pentahydroxy-3,5,3',5'-tetramethyl Hydroxytriphenylmethane such as triphenylmethane.

Further, as the acid chloride of naphthoquinonediazidesulfonic acid chloride or benzodiazepinediazidesulfonic acid chloride, etc., preferred is 1,2-naphthoquinonediazide-5-sulfonate. Base chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, and the like.

The radiation-sensitive composition of the present embodiment can be prepared by, for example, dissolving each component in a solvent to form a uniform solution, and then, if necessary, filtering it by, for example, a filter having a pore diameter of about 0.2 μm.

 [Characteristics of Radiation-Linear Compositions]  

The radiation sensitive composition of this embodiment can be used to form an amorphous film by spin coating. Further, the radiation sensitive composition of the present embodiment can be applied to a general semiconductor manufacturing process. Any of the positive resist pattern and the negative resist pattern may be formed depending on the type of the developing liquid to be used.

In the case of a positive resist pattern, the amorphous film formed by spin coating the radiation sensitive composition of the present embodiment has a dissolution rate of 5 Å/sec or less for the developing solution at 23 ° C. Good, 0.05~5Å/sec is better, 0.0005~5Å/sec is better. When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and can be easily used as a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. It is presumed that the solubility of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent component before and after exposure is dissolved in the exposed portion of the developing solution and insoluble in the developing solution. The contrast of the interface of the unexposed part becomes larger. And there is the effect of lowering the LER and reducing the defect.

In the case of a negative resist pattern, the amorphous film formed by spin coating the resist composition of the present embodiment preferably has a dissolution rate of 10 Å/sec or more for the developing solution at 23 ° C. . When the dissolution rate is 10 Å/sec or more, it is easily soluble in the developing solution and is suitable for the resist. Further, when the dissolution rate is 10 Å/sec or more, the resolution is improved. It is presumed that the minute surface portion of the resin containing the compound represented by the above formulas (1) and (2) and/or the compound as a constituent component dissolves and lowers the LER. There is also the effect of reducing the defect.

The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ° C for a predetermined period of time, and measuring the film thickness before and after the immersion by a known method such as a visual, ellipsometer or QCM method. .

In the case of a positive resist pattern, the amorphous film formed by spin-coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. After heating at 20 to 500 ° C, the exposure rate of the exposed portion to the developing solution at 23 ° C is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and more preferably 100 to 1000 Å / sec. . When the dissolution rate is above 10Å/sec, it is easily soluble in the developing solution and is more suitable for the resist. Moreover, when the dissolution rate is 10000 Å/sec or less, the resolution is improved. It is presumed that the compound represented by the above formulas (1) and (2) and/or the minute surface portion of the resin containing the compound as a constituent component are dissolved and the LER is lowered. There is also a defect reduction effect.

In the case of a negative resist pattern, the amorphous film formed by spin-coating the radiation sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. After heating at 20 to 500 ° C, the exposure speed of the exposed portion to the developing solution at 23 ° C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and more preferably 0.0005 to 5 Å / sec. . When the dissolution rate is 5 Å/sec or less, it is insoluble in the developing solution, and tends to be a resist. Further, when the dissolution rate is 0.0005 Å/sec or more, the resolution is improved. It is presumed that the solubility of the compound represented by the above formulas (1) and (2) and/or the resin containing the compound as a constituent component before and after exposure causes undissolved portions and undissolved in the developing solution. The interface contrast of the exposure portion of the developing liquid becomes large. There is also the effect of lowering the LER and reducing the defect.

 [ blending ratio of each component]  

In the radiation sensitive composition of the present embodiment, the content of the component (A) is used arbitrarily for the solid component (the component (A), the diazonaphthoquinone photoactive compound (B), and other components (D). The sum of the solid components, the same as the following), is preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, even more preferably from 10 to 90% by mass, particularly preferably from 25 to 75% by mass. In the radiation sensitive composition of the present embodiment, when the content of the component (A) is within the above range, a pattern having high sensitivity and a small roughness can be obtained.

In the radiation sensitive composition of the present embodiment, the content of the diazonaphthoquinone photoactive compound (B) is relative to the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B), and other components ( The sum of the solid components used in any of D) and the like is the same as the following, preferably from 1 to 99% by mass, more preferably from 5 to 95% by mass, even more preferably from 10 to 90% by mass, particularly preferably from 25 to 75. quality%. In the radiation sensitive composition of the present embodiment, when the content of the diazonaphthoquinone photoactive compound (B) is within the above range, a pattern having high sensitivity and a small roughness can be obtained.

 [Other ingredients (D)]  

In the radiation-sensitive linear composition of the present embodiment, one component other than the component (A) and the diazo-naphthoquinone photoactive compound (B) may be added as necessary in the range which does not inhibit the object of the present invention. Or two or more acid generators, crosslinking agents, acid diffusion control agents, dissolution promoters, dissolution control agents, sensitizers, surfactants, oxyacids or derivatives of organic carboxylic acids or phosphorus, heat and / or photohardening catalyst, polymerization inhibitor, flame retardant, filler, coupling agent, thermosetting resin, photocurable resin, dye, pigment, tackifier, lubricant, defoamer, leveling agent, Various additives such as an ultraviolet absorber, a surfactant, a colorant, and a nonionic surfactant. In addition, in this specification, the other component (D) is called arbitrary component (D).

In the radiation sensitive composition of the present embodiment, the blending ratio of each component (component (A) / diazonaphthoquinone photoactive compound (B) / optional component (D)) is based on the mass % of the solid component. It is preferably 1~99/99~1/0~98, more preferably 5~95/95~5/0~49, and even more preferably 10~90/90~10/0~10, and even better 20~80/80~20/0~5, especially good 25~75/75~25/0.

The blending ratio of each component is selected from each range so that the total of the components is 100% by mass. When the blending ratio of each component of the radiation sensitive composition of the present embodiment is in the above range, in addition to the roughness, the properties such as sensitivity and resolution tend to be excellent.

The radiation sensitive composition of the present embodiment may contain other resins without impairing the object of the present invention. Examples of such other resins include a novolac resin, a polyvinyl phenol, a polyacrylic acid, a polyvinyl alcohol, a styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinyl phenol as a monomer. The polymer of the unit or such derivatives. The blending amount of the resin may be appropriately adjusted depending on the type of the component (A) to be used, but it is preferably 30 parts by mass or less, more preferably 10 parts by mass, per 100 parts by mass of the component (A). Hereinafter, it is preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

 [Formation method of resist pattern]  

The method for forming a resist pattern according to the present embodiment includes: forming a photoresist layer on a substrate by using the resist composition or the radiation sensitive composition of the present embodiment, and then irradiating a predetermined region of the photoresist layer with radiation , the steps to perform the imaging. More specifically, the steps of forming a resist film on a substrate using the resist composition or the radiation sensitive composition of the present embodiment, and exposing the formed resist film, The step of developing the above resist film to form a resist pattern. The resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.

The method of forming the resist pattern is not particularly limited, and examples thereof include the following methods. First, the resist composition or the radiation sensitive composition is applied to a conventional substrate by a coating means such as spin coating, cast coating, or roll coating to form a resist film. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component or a predetermined wiring pattern. More specifically, for example, a metal substrate such as a tantalum wafer, copper, chromium, iron, or aluminum, or a glass substrate can be used. Examples of the material of the wiring pattern include copper, aluminum, nickel, gold, and the like. Further, an inorganic or/or organic film may be provided on the substrate as needed. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). The organic film may, for example, be an organic antireflection film (organic BARC). It is also possible to carry out surface treatment with hexamethylene diazane or the like.

Next, the substrate coated with the resist composition or the radiation-sensitive composition is heated as needed. Although the heating condition is changed depending on the composition of the resist composition or the radiation-sensitive composition, it is preferably 20 to 250 ° C, more preferably 20 to 150 ° C. It is preferable to increase the adhesion of the substrate of the resist by heating. Next, the resist film is exposed to a desired state by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. Graphic type. The exposure conditions and the like can be appropriately selected depending on the composition of the resist or the blending composition of the radiation-sensitive composition. In the present embodiment, in order to stably form a fine pattern having high precision during exposure, it is preferable to perform heating after irradiation with radiation. The heating condition varies depending on the composition of the resist agent or the radiation-sensitive composition, but is preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

Next, a predetermined resist pattern is formed by developing the exposed resist film as a developing solution. In terms of the developing solution, the solubility parameter (SP) of the resin obtained by using the compound represented by the formula (1) or the formula (2) or the compound represented by the formula (1) or the formula (2) as a monomer is selected. The solvent is preferably a similar solvent, and a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or an ether solvent, a hydrocarbon solvent or an aqueous alkali solution can be used.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl ketone. , cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetonyl acetone, ionone, diacetone, acetonitrile Alcohol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, and the like.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether. Acid ester, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Wait.

Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol. Alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol, or ethylene glycol, diethylene glycol a glycol solvent such as triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, A glycol ether solvent such as triethylene glycol monoethyl ether or methoxymethylbutanol.

Examples of the ether solvent include, in addition to the above glycol ether solvent, dioxane or tetrahydrofuran.

Examples of the amide-based solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, and 1, 3-dimethyl-2-tetrahydroimidazolium and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvents may be mixed in plural amounts, and may be used in combination with a solvent or water other than the above in the range of properties. However, in order to sufficiently achieve the effect of the present invention, the water content of the entire developing liquid is preferably less than 70% by mass, more preferably less than 50% by mass, more preferably less than 30% by mass, and less than 10% by mass. % is even better, and it is especially good for those who do not contain water. In other words, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less based on the total amount of the developing liquid, and more preferably 50% by mass or more and 100% by mass or less, and 70% by mass or more and 100% by mass or less. Further preferably, 90% by mass or more and 100% by mass or less are more preferably, and 95% by mass or more and 100% by mass or less are particularly preferable.

Examples of the aqueous alkali solution include mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), An alkaline compound such as choline.

In particular, from the viewpoint of improving the performance of the resist such as the resolution or the roughness of the resist pattern, the present invention contains a solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine system. A developing solution of at least one solvent of a solvent and an ether solvent is preferred.

The vapor pressure of the developing solution is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 kPa or less. When the vapor pressure of the developing solution is 5 kPa or less, evaporation of the liquid on the substrate of the developing solution or in the developing cup is suppressed, and the uniformity of temperature in the surface of the wafer is increased, and the dimensionality in the wafer surface is uniform. Sex will improve.

Examples of a specific developing solution having a vapor pressure of 5 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2- a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl antate, ethyl lactate, butyl lactate, lactate Ester solvent such as ester; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl An alcohol solvent such as benzyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; Glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, a glycol ether solvent such as triethylene glycol monoethyl ether or methoxymethylbutanol; an ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone and N,N-dimethylacetamide An amide-based solvent of N,N-dimethylformamide; an aromatic hydrocarbon solvent such as toluene or xylene; and an aliphatic hydrocarbon solvent such as octane or decane.

Examples of a specific developing solution having a vapor pressure of 2 kPa or less at 20 ° C include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, and 2- a ketone solvent such as ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone or phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxybutyl Ester acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, etc.; ester solvent; n-butyl alcohol, sec-butyl Alcohol solvent such as base alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-nonanol a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, two a glycol ether solvent such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol; N-methyl-2- Pyrrolidone, N,N-dimethylacetamide, guanamine solvent of N,N-dimethylformamide, aromatic hydrocarbon solvent such as xylene; aliphatic hydrocarbon system such as octane or decane Solvent.

In the developing solution, an appropriate amount of the surfactant may be added as needed. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or quinone-based surfactant can be used. For the fluorine and/or the lanthanide-based surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 5,057, 520, the specification of 5, 560, 692, the same as 5, 527, 988, the same as 5, 296, 730, the same as 5, 546, 998, the same as 5, 576, 143, the same as 5,294,511, the same as the description of the 5,842,451, A nonionic surfactant is preferred. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a lanthanoid surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass based on the total amount of the developing solution.

In the development method, for example, a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dipping method) can be applied by covering the surface of the substrate with a surface tension for a certain period of time and allowing it to stand. A method (a paddle stirrer method), a method of spraying a developing liquid on a surface of a substrate (spray method), and a developing solution is sprayed on a substrate rotating at a constant speed at a constant speed while scanning, and the image is discharged while scanning Liquid method (dynamic distribution method), etc. The time for performing the development of the pattern is not particularly limited, and is preferably from 10 seconds to 90 seconds.

Further, after the step of developing the image, the step of stopping the development may be performed instead of the other solvent.

After the development, it is preferred to carry out the step of washing with a washing liquid containing an organic solvent.

The washing liquid used in the washing step after the development is not particularly limited as long as the resist pattern which is cured by crosslinking is not dissolved, and a solution containing a general organic solvent or water can be used. In the washing liquid, it is preferred to use a washing liquid containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. More preferably, after the development, a washing liquid containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, or a guanamine solvent is used. More preferably, after the development, the step of washing with a washing liquid containing an alcohol solvent or an ester solvent is carried out. Further preferably, after the development, the step of washing with a washing liquid containing a monovalent alcohol is carried out. After the development is particularly preferred, the step of washing with a washing liquid containing a monovalent alcohol having 5 or more carbon atoms is carried out. The time for performing the pattern washing is not particularly limited, and is preferably from 10 seconds to 90 seconds.

Here, examples of the monovalent alcohol used in the washing step after development include a linear, branched, and cyclic monovalent alcohol. Specifically, 1-butanol or 2-butanol can be used. , 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octyl Alcohol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., particularly preferably having a carbon number of 5 or more As the monovalent alcohol, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol or the like can be used.

The above components may be mixed in plural amounts or may be used in combination with an organic solvent other than the above.

The water content in the washing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, more excellent development characteristics can be obtained.

The vapor pressure of the washing liquid used after the development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. When the vapor pressure of the washing liquid is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the washing liquid is suppressed, and the size in the wafer surface is uniform. Sex is better.

An appropriate amount of a surfactant may be added to the washing liquid for use.

In the washing step, the developed wafer is washed and washed using a cleaning solution containing the above organic solvent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously discharging the cleaning liquid on a substrate rotating at a constant speed (a spin coating method), and a method of immersing the substrate in a tank filled with the cleaning liquid for a predetermined period of time can be applied. (dipping method), a method of spraying a cleaning liquid on a surface of a substrate (spraying method), or the like, wherein the substrate is washed by a spin coating method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm to prepare a cleaning solution. It is preferred to remove from the substrate.

After the resist pattern is formed, the pattern wiring substrate can be obtained by etching. The etching method can be carried out by a conventional method such as dry etching of a plasma gas and wet etching such as an alkali solution, a copper chloride solution, or a ferric chloride solution.

After the formation of the resist pattern, plating can also be performed. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The residual resist pattern after etching can be peeled off by an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like. Examples of the peeling method include a dipping method, a spraying method, and the like. Further, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate or may have a small-diameter through hole.

The wiring board obtained in the present embodiment may be formed by forming a resist pattern, vapor-depositing the metal in a vacuum, and then melting the resist pattern into a solution, that is, by a lift-off method. .

 [Film forming composition for lithography of the underlying film use orientation]  

In the lithographic film forming composition (hereinafter referred to as "lower film forming material") for the use of the underlayer film in the present embodiment, the compound represented by the above formula (0) is represented by the above formula (0). The resin obtained as a monomer, the compound represented by the above formula (0-A), and the resin obtained by using the compound represented by the above formula (0-A) as a monomer, more specifically, the above formula (1) a compound obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the formula (2), and a resin obtained by using the compound represented by the formula (2) as a monomer. At least one substance selected from the group formed. In the present embodiment, the above-mentioned substance is preferably from 1 to 100% by mass, more preferably from 10 to 100% by mass, even more preferably from 50 to 100% by mass, from the viewpoint of coatability and quality stability. More preferably, 100% by mass is particularly good.

The underlayer film forming material of the present embodiment can be applied to a wet process and is excellent in heat resistance and etching resistance. In addition, in the layer film forming material of the present embodiment, since the above-mentioned substance is used, it is possible to form an underlayer film which is excellent in etching resistance at the time of high-temperature baking and excellent in etching resistance such as oxygen plasma etching. Further, the underlayer film forming material of the present embodiment is excellent in adhesion to the resist layer, and an excellent resist pattern can be obtained. Further, the layer film forming material of the present embodiment may contain a known underlayer film forming material for lithography, etc., without impairing the effects of the present invention.

 [solvent]  

The underlayer film forming material in the present embodiment may contain a solvent. The solvent used in the underlayer film forming material can be suitably used as long as the above substances are at least dissolved.

Specific examples of the solvent are not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; propylene glycol monomethyl ether and propylene glycol monomethyl ether B; Solvents such as acid esters; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, An ester solvent such as methyl hydroxyisobutyrate; an alcohol solvent such as methanol, ethanol, isopropanol or 1-ethoxy-2-propanol; or aromatic such as toluene, xylene or methylphenyl ether; Hydrocarbons, etc. These solvents may be used alone or in combination of two or more.

Among the above solvents, from the viewpoint of safety, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, methylbenzene The ethyl ether is particularly preferred.

The content of the solvent is not particularly limited, and is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, based on 100 parts by mass of the total mass of the solid component, from the viewpoint of solubility and film formation, and 200. ~1000 parts by mass is better.

 [crosslinking agent]  

The underlayer film forming material in the present embodiment may contain a crosslinking agent as needed from the viewpoint of suppressing layer mixing and the like. The crosslinking agent is not particularly limited, and for example, those described in International Publication No. 2013/024779 can be used.

Specific examples of the crosslinking agent which can be used in the embodiment include a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, an acrylate compound, a melamine compound, and a guanamine compound. A glycoluril compound, a urea compound, an isocyanate compound, an azide compound, or the like, but is not particularly limited thereto. These crosslinking agents may be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound or a cyanate compound is preferred, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.

As the above phenol compound, a conventional one can be used. For example, in addition to phenol, phenols include alkylphenols such as cresols and xylenols, polyvalent phenols such as hydroquinone, and naphthols and naphthalenediols. a bisphenol such as a cyclic phenol, a bisphenol A or a bisphenol F; or a polyfunctional phenol compound such as a phenol novolak or a phenol aralkyl resin. Among them, an aralkyl type phenol resin is preferred from the viewpoint of heat resistance and solubility.

As the epoxy compound, those skilled in the art can be used, and those having two or more epoxy groups in one molecule can be selected. For example, bisphenol A, bisphenol F, 3,3', 5,5'-tetramethyl-bisphenol F, bisphenol S, bisphenol, 2,2'-biphenol, 3,3', Bivalent phenolic epoxides of 5,5'-tetramethyl-4,4'-dihydroxybiphenol, resorcinol, naphthalenediol, etc., gins-(4-hydroxyphenyl)methane 1,1,2,2-indole (4-hydroxyphenyl)ethane, ginseng (2,3-epoxypropyl)isocyanate, trimethylolmethane triepoxypropyl ether a trivalent or higher phenolic epoxide such as trimethylolpropane triepoxypropyl ether, trishydroxyethylethane triepoxypropyl ether, phenol novolac, or o-cresol novolac, Epoxides, phenols and dichloroforms of phenolic aralkyl resins synthesized from epoxides of pentadiene and phenolic co-condensation resins, phenols and para-dimethylphenylene dichlorides An epoxy group of a naphthol aralkyl resin synthesized from an epoxide of a biphenyl aralkyl type phenol resin synthesized by a phenyl group or the like, a naphthol and a para-dimethylphenylene dichloride. Compounds, etc. These epoxy resins may be used singly or in combination of two or more. It is preferably a solid epoxy resin at room temperature, such as an epoxy resin obtained from a phenol aralkyl resin or a biphenyl aralkyl resin, from the viewpoint of heat resistance and solubility.

In the case of the cyanate ester compound, a compound having two or more cyanate groups in one molecule is not particularly limited, and a conventional one can be used. In the present embodiment, a preferred one of the cyanate ester compounds is a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group. Further, the cyanate ester compound is preferably an aromatic group, and it is preferred to use a structure in which a cyanate group is directly bonded to an aromatic group. Examples of such a cyanate ester compound include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolak resin, and dicyclopentadiene novolac. Resin, tetramethyl bisphenol F, bisphenol A novolak resin, brominated bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene phenol, biphenyl phenol, phenol aralkyl A structure in which a hydroxyl group such as a base resin, a biphenyl aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene aralkyl resin, an alicyclic phenol or a phosphorus-containing phenol is substituted with a cyanate group. These cyanate compounds may be used singly or in combination of two or more kinds as appropriate. Further, the cyanate ester compound may be in any form of a monomer, an oligomer, and a resin.

The above amine compound may, for example, be m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4' -diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3, 4'-Diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenylsulfide Ether, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2, 2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis (4 -aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[ 4-(3-Aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amino-3-chlorophenyl)anthracene, 9,9-bis(4-amino-3-fluorophenyl)anthracene, O-tolidine, m-tolidine, 4,4'-diaminobenzimidil, 2,2'-double (trifluoromethyl)- 4,4'-Diaminobiphenyl, 4-aminophenyl-4-aminobenzoate, 2-(4-aminophenyl)-6-aminobenzoxazole, and the like. Further, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diamino group Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4-double ( 4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3- Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-amino group An aromatic amine such as phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether or bis[4-(3-aminophenoxy)phenyl]ether; Diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] Heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6 An alicyclic ring of decane, 1,3-diaminomethylcyclohexane, isophorone diamine, etc. Amines, ethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, diethylene triamine, triethylene tetramine, etc. and the like aliphatic amines.

Examples of the benzoxazine compound include a F-type benzoxazole obtained from a Pd-type benzoxazine, a monofunctional diamine, and a difunctional phenol obtained from a difunctional diamine and a monofunctional phenol. And so on.

Specific examples of the above melamine compound include, for example, hexamethylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, 1-6 methylol methoxymethylated compounds or mixtures thereof 1 to 6 methoxymethylated compounds of hexamethoxyethyl melamine, hexamethoxymethyl melamine, hydroxymethyl hexamethylol melamine, or a mixture thereof.

Specific examples of the above guanamine compound include methoxymethylation of 1 to 4 methylol groups of tetramethylolguanamine, tetramethoxymethylguanamine, and tetrahydroxymethylguanamine. a compound or a mixture thereof, tetramethoxyethyl decylamine, tetradecyl decylamine, tetramethylol decylamine, 1 to 4 methylol groups, a methoxymethylated compound, or a mixture thereof .

Specific examples of the acetylene urea compound include, for example, 1 to 4 of hydroxymethyl groups of tetramethylol acetylene urea, tetramethoxy acetylene urea, tetramethoxymethyl acetylene urea, and tetramethylol acetylene urea. a methoxymethylated compound or a mixture thereof, 1 to 4 methoxymethylated compounds of a methylol group of tetramethylol acetylene urea, or a mixture thereof.

Specific examples of the urea compound may, for example, be a methoxymethylated compound of 1 to 4 methylol groups of tetramethylolurea, tetramethoxymethylurea or tetramethylolurea or Mixture, tetramethoxyethyl urea, and the like.

Further, in the present embodiment, a crosslinking agent having at least one allyl group can be used from the viewpoint of improving crosslinkability. Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3. -hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)anthracene, bis(3-allyl-4- Allyl phenol such as hydroxyphenyl) sulfide, bis(3-allyl-4-hydroxyphenyl)ether, 2,2-bis(3-allyl-4-cyanooxyphenyl) Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-cyanooxyphenyl)propane, bis(3-allyl-4-cyanide Allyl cyanide such as oxyphenyl) fluorene, bis(3-allyl-4-cyanooxyphenyl) sulfide, bis(3-allyl-4-cyanooxyphenyl) ether Ester, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl isocyanurate, trishydroxyl Propyl diallyl ether, pentaerythritol allyl ether, and the like, but are not limited by these examples. These may be used alone or in a mixture of two or more. Among these are 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-ene) Propyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)anthracene, bis(3-allyl-4-hydroxyphenyl) sulfide, bis(3-allyl Preferred are allyl phenols such as -4-hydroxyphenyl)ether.

The content of the crosslinking agent in the underlayer film forming material is not particularly limited, and the total mass of the solid component is preferably from 0.1 to 50% by mass, more preferably from 5 to 50% by mass, still more preferably from 10 to 40% by mass. When the content of the crosslinking agent is in the above range, there is a tendency to suppress the occurrence of a phenomenon of intermixing with the resist layer, and the antireflection effect is improved, and the film formability after crosslinking tends to be improved.

 [Crosslinking accelerator]  

In the layer film forming material of the present embodiment, a crosslinking accelerator for promoting crosslinking and curing reaction can be used as needed.

The cross-linking accelerator is not particularly limited as long as it promotes cross-linking or hardening reaction, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acids. These crosslinking accelerators may be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferred, and imidazoles are more preferable from the viewpoint of lowering the crosslinking temperature.

The cross-linking accelerator is not limited thereto, and examples thereof include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, and benzyldimethylamine. Tertiary amines such as triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5-triphenylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, An organic phosphine such as diphenylphosphine or phenylphosphine, tetraphenylphosphonium tetrakisborate, tetraphenylphosphonium, ethyltriphenylborate, tetrabutylphosphonium, tetrabutylborate or the like Tetraphenylphosphonium salts such as tetrasubstituted hydrazine, tetrasubstituted borate, 2-ethyl-4-methylimidazolium tetrakisborate, N-methylmorpholine, tetraphenylborate, and the like.

The content of the crosslinking accelerator is preferably from 0.1 to 10% by mass based on the total mass of the solid component, and more preferably from 0.1 to 5% by mass, and more preferably from 0.1 to 3, from the viewpoint of ease of control and economy. quality%.

 [Free radical polymerization initiator]  

In the underlayer film forming material of the present embodiment, a radical polymerization initiator may be blended as needed. The radical polymerization initiator may be a photopolymerization initiator which starts by radical polymerization by light, or a thermal polymerization initiator which starts radical polymerization by heat. The radical polymerization initiator may be, for example, at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator.

The radical polymerization initiator is not particularly limited, and a conventional user can be suitably used. For example, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxyl) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl) -benzyl]phenyl}-2-methylpropan-1-one, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethyl) Ketone-based photopolymerization initiators such as benzhydryl)-phenylphosphine oxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl ethyl Indole acetate peroxide, ethyl acetate acetate peroxide, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-double (t-hexylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butyl) Peroxy)-2-methylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, 1,1-bis(t-butylperoxy)cyclododecan Alkane, 1,1-bis(t-butylperoxy)butane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, p-menthane hydrogen peroxide Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl peroxidation , cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α,α'-bis(t-butylperoxy)diisopropylbenzene, diisopropylphenyl Oxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-Dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutylguanidino peroxide, 3,5,5-trimethylhexyl peroxide, octyl Peroxide, lauryl peroxide, stearic acid peroxide, succinic acid peroxide, m-tolylmethyl benzhydryl peroxide, benzhydryl peroxide, di-n -propylperoxydicarbonate, diisopropylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethylperoxy Dicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylperoxydicarbonate, two (3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(indenylperoxy)diisopropylbenzene, cumylperoxy new Phthalate, 1,1,3,3- Methyl butyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butylperoxy new Phthalate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid Ester, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t- Butylperoxy isobutyrate, t-butylperoxy malate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric Acid ester, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyacetate, t-butyl Oxy-m-tolylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2 , 5-bis(m-tolylperoxy)hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzylidene) Oxy)hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethyldecyl peroxide, 3,3',4,4'-tetra(t-butyl An organic peroxide-based polymerization initiator such as oxycarbonyl)benzophenone or 2,3-dimethyl-2,3-diphenylbutane.

Further, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and 1-[(1-cyano-1-methylethyl)azo]formin are also mentioned. Amine, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis ( 2-methyl-N-phenylpropionamidine dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydride chloride, 2 , 2'-azobis[N-(4-hydrophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[2-methyl-N-(phenylmethyl) Dihydrochloride, dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propene]dihydrochloride, 2,2'-azobis[N -(2-hydroxyethyl)-2-methylpropanthene]dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] Hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2 ' -azobis[2-(4,5,6, 7-tetrahydro-1H-1,3-diaza-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidine- 2-yl)propane]dihydrochloride, 2,2'-azobis[2-(5-hydroxy-3,4 ,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl Propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[2-methyl-N-[1 ,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl ]propionamine], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'-azobis(2-methylpropanamide ), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), dimethyl-2,2-azo Bis(2-methylpropionate), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[2-(hydroxymethyl)propionitrile, etc. An azo polymerization initiator. In the case of the radical polymerization initiator in the present embodiment, one type of these may be used alone or two or more types may be used in combination, and other conventional polymerization initiators may be further combined.

The content of the radical polymerization initiator may be 0.05 to 25% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the solid content. When the content of the radical polymerization initiator is 0.05% by mass or more, the curing tends to be insufficient, and when the content of the radical polymerization initiator is 25 parts by mass or less, the underlayer film forming material can be prevented from being present in the chamber. The long-term preservation of the tendency to damage stability.

 [acid generator]  

The underlayer film forming material in the present embodiment may contain an acid generator as needed from the viewpoint of further promoting a crosslinking reaction by heat or the like. As the acid generator, those which generate acid by thermal decomposition and which generate acid by light irradiation are known, but they can be used. For example, the one described in International Publication No. 2013/024779 can be used.

The content of the acid generator in the underlayer film forming material is not particularly limited, and is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 40% by mass, based on the total mass of the solid content. When the content of the acid generator is in the above range, the amount of acid generated tends to increase the amount of acid generated, and the crosslinking reaction tends to increase, and the phenomenon of suppressing intermixing with the resist layer tends to occur.

 [alkaline compound]  

The underlayer film forming material in the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound acts as a scavenger for the acid which prevents the acid generated by the acid generator from causing the crosslinking reaction to proceed. The basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.

The content of the basic compound in the underlayer film forming material is not particularly limited, and is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass based on the total mass of the solid content. When the content of the basic compound is in the above range, the storage stability can be improved without excessively damaging the crosslinking reaction.

 [Other additives]  

Further, the underlayer film forming material in the present embodiment may contain other resins and/or compounds for the purpose of imparting heat or light-based hardenability or controlling the absorbance. Examples of such other resins and/or compounds include a naphthol resin, a xylene resin naphthol modified resin, a phenol-modified resin of a naphthalene resin, a polyhydroxystyrene, a dicyclopentadiene resin, and a (meth) group. Included in the biphenyl ring, thiophene, anthracene, etc. of a naphthalene ring such as acrylate, dimethacrylate, trimethacrylate, tetramethacrylate, vinyl naphthalene or polydecene, phenanthrenequinone or anthracene a heterocyclic heterocyclic resin or an aromatic ring-free resin; a rosin-based resin, a cyclodextrin, an adamantane (poly)ol, a tricyclodecane (poly)ol, and the like The resin or compound of the ring structure is not particularly limited as such. Further, the underlayer film forming material in the present embodiment may contain a conventional additive. The conventional additive is not limited, and may, for example, be a heat and/or photohardening catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photocurable resin, or a dye. , pigments, tackifiers, lubricants, defoamers, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.

 [Formation method of underlayer film and multilayer resist pattern for lithography]  

The underlayer film for lithography in the present embodiment can be formed of the underlayer film forming material.

Further, in the resist pattern forming method of the present embodiment, the lower layer film is formed on the substrate by using the composition, and at least one photoresist layer is formed on the underlayer film, and then the photoresist layer is formed on the photoresist layer. The step of imaging by irradiating radiation in a predetermined area. More specifically, the step (A-1) of forming a lower film using the underlayer film forming material of the present embodiment on the substrate, and forming at least one photoresist layer on the underlayer film. In the step (A-2) and the step (A-2), the step (A-3) of developing radiation on a predetermined region of the photoresist layer is performed.

Furthermore, the circuit pattern forming method of the present embodiment includes the steps of forming a lower layer film on a substrate using the composition, and forming an intermediate layer film on the underlying film using a resist intermediate layer film material, and a step of forming at least one photoresist layer on the intermediate layer film, irradiating radiation to a predetermined region of the photoresist layer, and developing a resist pattern, and etching the resist pattern as a mask In the intermediate layer film, the obtained intermediate layer film pattern is used as an etching mask to etch the underlying film, and the obtained underlying film pattern is used as an etching mask etching substrate, thereby forming a pattern on the substrate.

More specifically, there is a step of forming a lower film by using the underlayer film forming material of the present embodiment on the substrate (B-1), and using a resist intermediate layer containing germanium atoms on the underlying film. a step (B-2) of forming an interlayer film by a film material, a step (B-3) of forming at least one photoresist layer on the interlayer film, and a step (B-3) after the step After the predetermined area of the layer is irradiated with radiation, and the step (B-4) of forming the resist pattern is formed, and the step (B-4) is performed, the resist pattern is used as a mask to etch the interlayer film, and the intermediate layer film is etched. The obtained interlayer film pattern is used as an etching mask to etch the underlayer film, and the resulting underlayer film pattern is used as an etching mask etching substrate to form a pattern on the substrate (B-5).

The underlayer film for lithography in the present embodiment is not particularly limited as long as it is formed of the underlayer film forming material, and a conventional method can be applied. For example, the layer film material of the present embodiment is applied to the substrate by a conventional coating method such as spin coating or screen printing, or a printing method, and the organic solvent is removed by volatilization or the like. A known method for crosslinking and hardening can form the underlayer film for lithography of the present embodiment. The crosslinking method may, for example, be a method such as thermal curing or photocuring.

At the time of formation of the underlayer film, it is preferred to carry out baking in order to suppress the occurrence of the mutual mixing phenomenon with the upper layer resist while promoting the crosslinking reaction. At this time, the baking temperature is not particularly limited, and is preferably in the range of 80 to 450 ° C, more preferably 200 to 400 ° C. Further, the baking time is not particularly limited, but it is preferably in the range of 10 to 300 seconds. Further, the thickness of the underlayer film can be appropriately selected according to the required performance, and is not particularly limited, and is usually about 30 to 20,000 nm, more preferably 50 to 15,000 nm.

After the underlayer film is formed, a two-layer resist composed of a ruthenium-containing resist layer or a general hydrocarbon is formed on the two-layer process, and a ruthenium-containing intermediate layer is formed thereon in the three-layer process. Further, it is preferred to form a single-layer resist layer containing no antimony thereon. At this time, a conventional one can be used for forming the photoresist material for the resist layer.

After the underlayer film is formed on the substrate, a resist layer containing ruthenium or a general single layer resist composed of hydrocarbons can be formed on the underlayer film during the two-layer process. In the 3-layer process, an intermediate layer containing ruthenium may be formed on the underlayer film, and a single-layer resist layer containing no ruthenium may be further formed on the intermediate layer containing the ruthenium. In such a case, the photoresist material for forming the resist layer can be appropriately selected and used by a person skilled in the art, and is not particularly limited.

In the case of the ruthenium-containing resist material for the two-layer process, it is preferable to use a ruthenium atom-containing polymer such as a polysilsesquioxane derivative or a vinyl decane derivative as a matrix polymer from the viewpoint of oxygen etching resistance. Further, it further contains a positive resistive material such as an organic solvent, an acid generator, or a basic compound as needed. As the polymer containing a halogen atom, a conventional polymer used in such a resist material can be used.

For the intermediate layer containing ruthenium for the three-layer process, it is preferred to use an intermediate layer of polysilsesquioxane. By providing the intermediate layer with an effect as an antireflection film, there is a tendency that reflection can be effectively suppressed. For example, in the 193 nm exposure process, when a material containing a large amount of aromatic groups and high substrate etching resistance is used as the underlayer film, the k value tends to be high and the substrate reflection tends to be high. However, the substrate can be suppressed by reflection with the intermediate layer. The reflection is below 0.5%. The intermediate layer having such an antireflection effect is not limited to the following, but it is preferable to use a polyp-half which is crosslinked by acid or heat by introducing a phenyl group or a light-absorbing group having a fluorene-矽 bond for 193 nm exposure. Oxane.

Further, an intermediate layer formed by a Chemical Vapour Deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. In general, the formation of an intermediate layer in a wet process such as spin coating or screen printing is simple and cost-effective compared to the CVD method. Further, the upper layer resist in the three-layer process may be either positive or negative, and may be the same as the single-layer resist which is generally used.

Further, the underlayer film of the present embodiment can also be used as a general antireflection film for a single layer resist or an underlayer material for suppressing collapse of a pattern. Since the underlayer film of the present embodiment is excellent in etching resistance for the underlayer processing, it is expected to function as a hard mask for underlayer processing.

When the resist layer is formed of the above-mentioned photoresist material, it is preferable to use a wet process such as a spin coating method or screen printing as in the case of forming the underlayer film. After the resist material is applied by spin coating or the like, prebaking is usually carried out, and the prebaking is preferably carried out at 80 to 180 ° C for 10 to 300 seconds. Thereafter, exposure is carried out in accordance with a conventional method, and by post-exposure baking (PEB), development, whereby a resist pattern can be obtained. The thickness of the resist film is not particularly limited and is usually from 30 to 500 nm, more preferably from 50 to 400 nm.

Further, the exposure light can be appropriately selected and used depending on the photoresist material to be used. Generally, for example, a high-energy line having a wavelength of 300 nm or less, specifically, a quasi-molecular laser of 248 nm, 193 nm, and 157 nm, a soft X-ray of 3 to 20 nm, an electron beam, an X-ray, or the like can be given.

The resist pattern formed by the above method is a pattern in which the pattern collapse is suppressed by the underlayer film in the present embodiment. Therefore, by using the underlayer film in the present embodiment, a finer pattern can be obtained, and the amount of exposure necessary for obtaining the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. In the etching of the underlying film in the 2-layer process, gas etching is preferably used. In terms of gas etching, etching using oxygen is preferred. In addition to oxygen, an inert gas such as He or Ar or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ or H _{2 may be added} . Further, it is also possible to perform gas etching using only CO, CO ₂ , NH ₃ , N ₂ , NO ₂ , and H ₂ gas without using oxygen. In particular, the latter gas is preferably used to prevent sidewall protection for undercutting of the sidewalls of the pattern.

On the other hand, in the etching of the intermediate layer in the 3-layer process, gas etching is also preferably used. The gas etching can be applied to the same as those described in the above two-layer process. In particular, it is preferred that the intermediate layer in the three-layer process be processed using a Freon-based gas and a resist pattern as a mask. Thereafter, as described above, the intermediate layer pattern is used as a mask, and for example, oxygen etching is performed, whereby the underlayer film can be processed.

Here, in the case where an inorganic hard mask intermediate layer film is formed as an intermediate layer, a tantalum oxide film, a tantalum nitride film, or a tantalum oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method of forming the nitride film is not limited, and methods described in, for example, JP-A-2002-334869 (Patent Document 6) and WO2004/066377 (Patent Document 7) can be used. Although a photoresist film can be directly formed on such an interlayer film, an organic anti-reflection film (BARC) can be formed by spin coating on the interlayer film, and a photoresist film can be formed thereon.

By making the resist interlayer film have an effect as an antireflection film, there is a tendency that reflection can be effectively suppressed. The specific material of the intermediate layer of the poly-sesquiterpene oxyalkyl group is not limited, and for example, JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9) can be used. Recorder.

The subsequent etching of the substrate can also be carried out by a general method. For example, if the substrate is SiO ₂ or SiN, etching with a Freon-based gas as the main component, p-Si or Al, and W can be carried out for chlorine or bromine. The gas is the main body etching. When the substrate is etched with a Freon-based gas, the ruthenium-containing resist of the two-layer resist process and the intermediate layer containing the ruthenium of the three-layer process are simultaneously peeled off. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the delamination of the ruthenium-containing resist layer or the ruthenium-containing intermediate layer is additionally performed, and after the substrate is processed, dry etching is performed by a Freon-based gas.

The underlayer film in the present embodiment has characteristics in which the etching resistance of these substrates is excellent. Further, the substrate can be suitably selected from conventional ones, and is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. Further, the substrate may be a laminate having a film to be processed (substrate to be processed) on a substrate (support). Examples of the film to be processed include Low-k film of Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and the like. For the film or the like, a material different from the substrate (support) is usually used. Further, the thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually about 50 to 10,000 nm, more preferably 75 to 5,000 nm.

 [Resistance permanent film]  

In addition, the above composition can also be used to form a permanent film of a resist, and the permanent film of the resist formed by applying the above composition can be used as a resist pattern and as a permanent residue in the final product. membrane. Specific examples of the permanent film include, in the field of semiconductor devices, a package adhesion layer such as a solder resist, a package material, a underfill material, and a circuit component, or an adhesive layer of a circuit board component and a circuit substrate. Examples are thin film transistor protective films, liquid crystal color filter protective films, black matrices, spacers, and the like. In particular, the permanent film composed of the above composition is excellent in heat resistance and moisture resistance, and also has an advantage that the sublimation component is less excellent in contamination. In particular, in the display material, it is a material having high sensitivity, high heat resistance, and moisture absorbing reliability which are less deteriorated in image quality due to important contamination.

When the above composition is used for a resist permanent film application, in addition to the hardener, various additives such as other resins, surfactants or dyes, fillers, crosslinking agents, dissolution promoters, etc. may be added as needed. In the organic solvent, it can be used as a resistive permanent film composition.

The composition for forming a film for lithography or the composition for a permanent film of a resist can be adjusted by blending the above components and mixing them using a stirrer or the like. Further, when the composition for a resist underlayer film or the composition for a resist permanent film contains a filler or a pigment, it can be adjusted by dispersing or mixing using a dispersing device such as a dissolving device, a homogenizer, or a three-roll mill. .

 [Examples]  

Hereinafter, the present embodiment will be described in detail by way of synthesis examples, synthesis examples, examples, and comparative examples, but the embodiment is not limited to these examples.

 (carbon concentration and oxygen concentration)  

The carbon concentration and the oxygen concentration (% by mass) were measured by organic element analysis using the following apparatus.

Device: CHN CORDER MT-6 (Yanako Analytical Industry Co., Ltd.)

 (molecular weight)  

The molecular weight of the compound was measured by LC-MS analysis using Acquity UPLC/MALDI-Synapt HDMS manufactured by Water Corporation.

Further, colloidal permeation chromatography (GPC) analysis was carried out under the following conditions to obtain a weight average molecular weight (Mw), a number average molecular weight (Mn), and a dispersity (Mw/Mn) in terms of polystyrene.

Device: Shodex GPC-101 (Showa Denko (share) system)

Column: KF-80M×3

Dissolved solution: THF 1mL/min

Temperature: 40 ° C

 (solubility)  

The compound is made at 23 ° C relative to propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), methyl amyl ketone (MAK) or tetramethyl urea (TMU). After stirring and dissolving in a 3 wt% or 10 mass% solution, the result after one week was evaluated on the basis of the following.

Evaluation S: It was visually confirmed by a 10% by mass solution that no precipitate was formed in any of the solvents.

Evaluation A: It was visually confirmed by a 3% by weight solution that no precipitate was formed in any of the solvents.

Evaluation C: It was visually confirmed that all the solvents were precipitated.

 [Construction of Compounds]  

The structure of the compound was measured by ¹ H-NMR measurement using the "Advance 600 II spectrometer" manufactured by Bruker Co., Ltd., and confirmed.

Frequency: 400MHz

Solvent: d6-DMSO

Internal standard: TMS

Measuring temperature: 23 ° C

 <Synthesis Example 1> Synthesis of BiN-1  

In a container having a volume of 300 mL of a stirrer, a cooling tube, and a burette, 10 g (69.0 mmol) of 2-naphthol (a reagent manufactured by Sigma-Aldrich Co., Ltd.) was melted at 120 ° C, and then 0.27 g of sulfuric acid was placed, and 4- Ethyl phenyl biphenyl (a reagent manufactured by Sigma-Aldrich Co., Ltd.) was 2.7 g (13.8 mmol), and the content was stirred at 120 ° C for 6 hours to carry out a reaction to obtain a reaction liquid. Next, 100 mL of N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) and 50 mL of pure water were added to the reaction mixture, followed by extraction with ethyl acetate. Further, pure water was added until liquid separation was carried out, and then concentrated to obtain a solution.

After the obtained solution was separated by a column chromatography layer, the objective compound (BiN-1) represented by the following formula (BiN-1) was obtained as 1.0 g.

The result of measuring the molecular weight of the obtained compound (BiN-1) by the above method was 466.

The obtained compound (BiN-1) was subjected to NMR measurement under the above-mentioned measurement conditions. As a result, the following peaks were observed, and the chemical structure of the following formula (BiN-1) was confirmed.

δ (ppm) 9.69 (2H, O-H), 7.01~7.67 (21H, PH-H), 2.28 (3H, C-H)

 <Synthesis Example 2> Synthesis of BiP-1  

The target compound represented by the following formula (BiP-1) was obtained in an amount of 0.1 g, except that 2,2'-biphenol was used instead of 2-naphthol.

The result of measuring the molecular weight of the obtained compound (BiP-1) by the above method was 466.

When the NMR measurement was carried out on the obtained compound (BiP-1) under the above-mentioned measurement conditions, the following peaks were observed, and the chemical structure of the following formula (BiP-1) was confirmed.

δ (ppm) 9.40 (4H, O-H), 6.80~7.80 (23H, Ph-H), 2.25 (3H, C-H)

 <Synthesis Example 1-1> Synthesis of Al-BiN-1  

To a vessel having a volume of 100 ml containing a stirrer, a cooling tube and a burette, 9.8 g (21 mmol) of the compound represented by the above formula (BiN-1) and 6.2 g (45 mmol) of potassium carbonate were added to 100 mL of acetone. The liquid was further added with bromoallyl 5.4 (45 mmol) g and 2.0 g of 10-crown-6, and the resulting reaction mixture was stirred under reflux for 7 hours to carry out a reaction. Next, the solid component was removed from the reaction liquid by filtration, cooled in an ice bath, and the reaction liquid was concentrated to precipitate a solid matter. After the precipitated solid matter was filtered and dried, it was separated and purified by column chromatography to obtain 3.8 g of the objective compound of the formula (Al-BiN-1).

The result of measuring the molecular weight of the obtained compound (Al-BiN-1) by the above method was 546.

The obtained compound had a thermal decomposition temperature of 370 ° C and a glass transition temperature of 90 ° C, and it was confirmed that it had high heat resistance.

The obtained compound (Al-BiN-1) was subjected to NMR measurement under the above-mentioned measurement conditions. As a result, the following peaks were observed, and the chemical structure of the following formula (Al-BiN-1) was confirmed.

δ (ppm) 6.98~7.60 (25H, Ph-H), 5.90 (2H, -CH=CH2), 4.90 (4H, -CH=CH2), 3.80 (4H, -CH2-), 2.25 (3H, CH)

 <Synthesis Example 2-1> Synthesis of Al-BiP-1  

The target compound represented by the following formula (Al-BiP-1) was obtained in an amount of 2.9 g, except that BiP-1 was used in the same manner as in the synthesis of Example 1-1.

The result of measuring the molecular weight of the obtained compound (Al-BiP-1) by the above method was 710.

The obtained compound had a thermal decomposition temperature of 380 ° C and a glass transition temperature of 180 ° C, and it was confirmed that it had high heat resistance.

The obtained compound (Al-BiP-1) was subjected to NMR measurement under the above-mentioned measurement conditions. As a result, the following peaks were observed, and the chemical structure of the following formula (Al-BiP-1) was confirmed.

δ (ppm) 9.4 (4H, OH), 6.8 to 7.8 (23H, Ph-H), 5.90 (4H, -CH=CH ₂ ), 4.90 (8H, -CH=CH ₂ ), 3.80 (8H, -CH) ₂ -), 2.25 (3H, CH)

 <Synthesis Example 1-2> Synthesis of AlOH-BiN-1  

6.1 g (11 mmol) of the compound represented by the above formula (Al-BiN-1) was added to 6.0 mL of a vessel having a volume of 100 ml of a stirrer, a cooling tube and a burette, and the reaction solution was stirred at 130 ° C for 6 hours. Thereafter, the temperature was raised to 160 ° C for 24 hours. Next, 30 mL of water was added to the reaction liquid to precipitate crystals, which were separated by filtration. The obtained solid matter was filtered and dried, and then purified by column chromatography to give 0.72 g of the desired compound. The chemical structure having the following formula was confirmed by 400 MHz - ¹ H-NMR.

The result of measuring the molecular weight of the obtained compound (AlOH-BiN-1) by the above method was 546.

The obtained compound had a thermal decomposition temperature of 370 ° C and a glass transition temperature of 100 ° C, and it was confirmed that it had high heat resistance.

The obtained compound (AlOH-BiN-1) was subjected to NMR measurement under the above-mentioned measurement conditions. As a result, the following peaks were observed, and the chemical structure of the following formula (AlOH-BiN-1) was confirmed.

δ (ppm) 9.78 (2H, OH), 7.01 to 7.67 (19H, Ph-H), 5.90 (2H, -CH=CH ₂ ), 4.90 (4H, -CH=CH ₂ ), 3.80 (4H, -CH) ₂ -), 2.28 (3H, CH)

 <Synthesis Example 2-2> Synthesis of AlOH-BiP-1  

In the same manner as in the synthesis example 1-2 except that Al-BiP-1 was used instead of Al-BiN-1, the objective compound represented by the following formula (AlOH-BiP-1) was 0.9 g. .

The obtained compound (AlOH-BiP-1) was found to have a molecular weight of 710 by the above method.

The obtained compound had a thermal decomposition temperature of 385 ° C and a glass transition temperature of 190 ° C, and it was confirmed that it had high heat resistance.

The obtained compound (AlOH-BiP-1) was subjected to NMR measurement under the above-mentioned measurement conditions. As a result, the following peaks were observed, and the chemical structure of the following formula (AlOH-BiP-1) was confirmed.

δ (ppm) δ (ppm) 9.4 (4H, OH), 6.8 to 7.8 (19H, Ph-H), 5.9 (4H, -CH=CH ₂ ), 4.9 (8H, -CH=CH ₂ ), 3.8 ( 8H, -CH ₂ -), 2.25 (3H, CH)

 (Synthesis Example 3 to 13)  

The raw materials of 2-naphthol and 4-ethylindenylbiphenyl of Synthesis Example 1 were changed as shown in Table 1, and the others were carried out in the same manner as in Synthesis Example 1, to obtain each object.

Each was identified by 1H-NMR (Table 2).

 (Synthesis examples 14 to 15)  

The raw materials of the synthesis examples were 2-naphthol and 4-ethenylbiphenyl. The raw materials 1 and 2 of Table 3 were changed, and 1.5 mL of water, 73 mg (0.35 mmol) of dodecyl mercaptan, and 2.3% hydrochloric acid were added. g (22 mmol), and the reaction temperature was changed to 55 ° C, and the other system was carried out in the same manner as in Synthesis Example 1, to obtain each object. Each was identified by 1H-NMR (Table 4).

 (Synthesis Examples 3-1 to 15-1)  

The compound represented by the above formula (BiN-1) which is a raw material of Synthesis Example 1-1 was changed as shown in Table 5, and the other was synthesized under the same conditions as in Synthesis Example 1-1, and each of them was obtained. The structure of each compound was determined by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS, and was identified by this.

 (Synthesis Example 3-2 to 15-2)  

The compound represented by the above formula (Al-BiN-1) which is a raw material of Synthesis Example 1-2 was changed as shown in the starting material 1 of Table 5, and the other compounds were synthesized under the same conditions as in Synthesis Example 1-2. Obtain the target. The structure of each compound was confirmed by 400 MHz- ¹ H-NMR (d-DMSO, internal standard TMS) and LC-MS, and was identified by this.

 (Synthesis Example 16) Synthesis of Resin (R1-BiP-1)  

A four-necked flask of 1 L in volume with a Deer condenser tube, a thermometer, and a stirring blade was prepared. In the four-necked flask, 36.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 21.0 g of a 40% by mass aqueous solution of Formalin (formaldehyde: 280 mmol) of the compound (BiP-1) obtained in Synthesis Example 2 were placed under a nitrogen atmosphere. It is 0.97 mL of 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) and reacted at 100 ° C under normal pressure for 7 hours under reflux. Then, 180.0 g of o-xylene (Special grade of Wako Pure Chemical Industries, Ltd.) was added as a diluent solvent to the reaction liquid, and the aqueous phase of the lower phase was removed after standing. Further, the mixture was neutralized and washed with water, and o-xylene was distilled off under reduced pressure to obtain 34.1 g of a brown solid resin (R1-BiP-1).

The obtained resin (R1-BiP-1) was Mn: 1875, Mw: 3550, and Mw/Mn: 1.89.

 (Synthesis Example 17) Synthesis of Resin (R2-BiP-1)  

A four-necked flask containing a 1 L inner volume with a Deer condenser tube, a thermometer, and a stirring blade was prepared. In the four-necked flask, 36.6 g (70 mmol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 4-diphenylaldehyde 50.9 g (280 mmol, Mitsubishi Gas Chemicals) of the compound (BiP-1) obtained in Synthesis Example 2 was placed under a nitrogen stream. 100 mL of methylphenyl ether (manufactured by Kanto Chemical Co., Ltd.) and 10 mL of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Ltd.), and reacted at 100 ° C under reflux under normal pressure. 7 hours. Then, 180.0 g of o-xylene (Special grade of Wako Pure Chemical Industries, Ltd.) was added as a diluent solvent to the reaction liquid, and the aqueous phase of the lower phase was removed after standing. Further, the mixture was neutralized and washed with water, and the solvent of the organic phase and the unreacted 4-biphenylaldehyde were distilled off under reduced pressure to obtain 34.7 g of a brown solid resin (R2-BiP-2).

The obtained resin (R2-BiP-2) was Mn: 1682, Mw: 2910, and Mw/Mn: 1.73.

 <Synthesis Example 16-1> Synthesis of Al-R1-BiP-1  

Into a container having a volume of 500 ml of a stirrer, a cooling tube, and a burette, 29.8 g of the resin represented by the above formula (R1-BiP-1) and 6.2 g (45 mmol) of potassium carbonate were added to 200 ml of acetone. Further, 5.4 g (45 mmol) of brominated allyl group and 2.0 g of 10-crown-6 were added to the liquid, and the resulting reaction solution was stirred under reflux for 7 hours to carry out a reaction. Then, the solid component was removed from the reaction liquid by filtration, and the reaction liquid was cooled and concentrated in an ice bath, and the solid was precipitated, filtered, and dried to obtain 35.6 g of a brown solid resin (Al-R1-BiP-1).

The obtained resin (Al-R1-BiP-1) was Mn: 2299, Mw: 3982, and Mw/Mn: 1.73.

 <Synthesis Example 16-2> Synthesis of AlOH-R1-BiP-1  

In a container having a 500 ml inner volume of a stirrer, a cooling tube, and a burette, 26.1 g of the resin represented by the above formula (Al-R1-BiP-1) was added to 30.0 mL of N-methylpyrrolidone, and the reaction was stirred at 130 ° C. The solution was allowed to stand for 6 hours, and then heated to 160 ° C for 24 hours. Further, 150 mL of water was added to the reaction mixture to precipitate a solid, which was separated by filtration. The obtained solid matter was filtered and dried to obtain 32.4 g of a resin represented by the following formula: AlOH-R1-BiP-1 as a brown solid.

The obtained resin (AlOH-R1-BiP-1) was Mn: 2216, Mw: 3845, and Mw/Mn: 1.73.

 <Synthesis Example 17-1> Synthesis of Al-R2-BiP-1  

Into a container having a 500 ml inner volume of a stirrer, a cooling tube, and a burette, 29.8 g of the resin represented by the above formula (R2-BiP-1) and 6.2 g (45 mmol) of potassium carbonate were added to 200 ml of acetone. Further, 5.4 g (45 mmol) of brominated allyl group and 2.0 g of 10-crown-6 were added to the liquid, and the resulting reaction mixture was stirred under reflux for 7 hours to carry out a reaction. Then, the solid component was removed from the reaction liquid by filtration, and the reaction liquid was cooled and concentrated in an ice bath, and the solid was precipitated, filtered, and dried to obtain 37.4 g of a brown solid resin (Al-R2-BiP-1).

The obtained resin (Al-R2-BiP-1) was Mn: 2630, Mw: 4682, and Mw/Mn: 1.78.

 <Synthesis Example 17-2> Synthesis of AlOH-R2-BiP-1  

The reaction was carried out in the same manner as in Synthesis Example 16-2 except that 29.8 g of the resin represented by the above formula (Al-R2-BiP-1) was used instead of the resin represented by the above formula (R2-BiP-1). 22.4 g of a resin represented by the following formula AlOH-R2-BiP-1 as a brown solid was obtained.

The obtained resin (AlOH-R2-BiP-1) was Mn: 2712, Mw: 4641, Mw/Mn: 1.71.

 (Synthesis Comparative Example 1)  

A four-necked flask of 10 L in volume with a Deer condenser tube, a thermometer and a stirring blade was prepared. In this four-necked flask, 1,9 kg of 1,5-dimethylnaphthalene (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 2.1 kg of a 40% by mass aqueous solution of Formalin were placed under a nitrogen flow (as a formaldehyde of 28 mol, Mitsubishi Gas Chemical ( (manufactured by the company) and 0.97 mL of 98% by mass of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), and reacted at 100 ° C for 7 hours under reflux at normal pressure. Then, 1.8 kg of ethylbenzene (Special grade of the reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a diluent solvent to the reaction liquid, and the aqueous phase of the lower phase was removed after standing. Further, the mixture was neutralized and washed with water, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure, whereby 1.25 kg of dimethylnaphthalene formaldehyde resin as a pale brown solid was obtained.

The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.

Next, a four-necked flask equipped with a volume of 0.5 L of a condenser tube, a thermometer, and a stirring blade was prepared. Into a four-necked flask, 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin obtained above and 0.05 g of p-toluenesulfonic acid were placed under a nitrogen stream, and the mixture was heated to 190 ° C for 2 hours, and then stirred. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the mixture was further heated to 220 ° C to carry out a reaction for 2 hours. After the solvent was diluted, it was neutralized and washed with water, and the solvent was removed under reduced pressure to obtain 126.1 g of a dark brown solid modified resin (CR-1).

The obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw/Mn: 4.17. Further, the carbon concentration was 89.1% by mass and the oxygen concentration was 4.5% by mass.

 [Examples 1-1 to 17-2, Comparative Example 1]  

The compounds and the resins of the above Synthesis Examples 1-1 to 17-2 and the resin CR-1 of Comparative Synthesis Example 1 were evaluated for solubility. The results are shown in Table 6 below.

Further, the lithographic underlayer film forming materials each having the composition shown in Table 1 were prepared. Then, these lithograms were spin-coated on the ruthenium substrate with the underlayer film forming material, and then baked at 240 ° C for 60 seconds and then at 400 ° C for 120 seconds to form a layer having a film thickness of 200 nm. membrane. The acid generator, the crosslinking agent, and the organic solvent are used as described later.

‧ Acid generator: T-butyl diphenyl sulfonium nonafluoromethane sulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.

‧ Crosslinker: NIKALAC MX270 (NIKALAC), manufactured by Sanwa Chemical Co., Ltd.

‧Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

Further, each of the underlayer film forming materials for lithography having the composition shown in Table 7 below was prepared. Then, these lithograms were spin-coated on the ruthenium substrate with the underlayer film forming material, and then baked at 110 ° C for 60 seconds to remove the solvent of the coating film, and then the high-pressure mercury lamp was used to calculate the exposure amount of 600 mJ/cm ^{2 .} The irradiation time was hardened for 20 seconds, and a film having a film thickness of 200 nm was formed. The photoacid generator, crosslinker and organic solvent are as set forth in Table 76.

‧Photoacid generator: WPAG-336 (diphenyl-4-methylphenyl fluorene trifluoromethanesulfonate)

‧ Crosslinker:

Mitsubishi Gas Chemically Made Diallyl Bisphenol A Type Cyanate (DABPA-CN)

Xiaoxi Chemical Industry, diallyl bisphenol A (BPA-CA)

Xiaoxi Chemical Industry Benzoxazine (BF-BXZ)

Nippon Chemical Co., Ltd. Biphenyl aralkyl type epoxy resin (NC-3000-L)

‧Organic solvents:

Propylene glycol monomethyl ether acetate acetate (PGMEA)

The structure of the above crosslinking agent is represented by the following formula.

(In the above formula, n is an integer from 1 to 4).

(NC-3000-L)

 [etching resistance]  

The etching test was performed under the conditions shown below, and the etching resistance was evaluated. The evaluation results are shown in Tables 6 and 7.

 [etching test]  

Etching device: RIE-10NR manufactured by SAMCO

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

Ar gas flow: CF ₄ gas flow: O ₂ gas flow = 50: 5: 5 (sccm)

The evaluation of the etching resistance was carried out by the following procedure.

First, a layer film of a novolac layer was produced under the same conditions as in Example 1-1 except that a novolak (PSM4357 manufactured by Kyoei Chemical Co., Ltd.) was used instead of the compound (Al-BisN-1). Further, the above etching test was carried out on the underlayer film of the novolac, and the etching rate at that time was measured.

Next, in the examples 1-1 to 17-2, 1-1A to 17-2A, and the underlayer film of Comparative Example 1, the etching test was carried out in the same manner, and the etching rate at that time was measured.

Moreover, the etching resistance was evaluated based on the following evaluation criteria based on the etching rate of the underlayer film of the novolak.

 [evaluation benchmark]  

A: The etching rate is less than -10% compared to the film under the aldehyde varnish.

B: The etching rate is -10% to +5% compared to the film under the aldehyde varnish.

C: The etching rate is more than +5% compared to the film under the aldehyde varnish.

As is clear from Tables 6 and 7, it is confirmed that the examples of the underlayer forming material containing the compound of the present embodiment are good at any of solubility and etching resistance. Further, in Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin), the etching resistance was poor.

Further, as described above, the compounds of the examples are excellent in heat resistance.

 (Examples 38 to 41)  

Next, each solution containing the underlayer film forming material of lithography containing Al-BiN-1, Al-BiP-1, AlOH-BiN-1 or AlOH-BiP-1 was applied onto a SiO ₂ substrate having a thickness of 300 nm. The film was formed to have a film thickness of 70 nm by baking at 240 ° C for 60 seconds and then at 400 ° C for 120 seconds. A resist solution for ArF was applied onto the underlayer film, and baked at 130 ° C for 60 seconds to form a photoresist layer having a film thickness of 140 nm. Further, in the case of the ArF resist solution, a compound in which the following formula (11) is blended is used: 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, and tributylamine: 2 parts by mass And PGMEA: 92 parts by mass.

The compound of the following formula (11) is 4.15 g of 2-methyl-2-methylpropenyloxyadamantane, 3.00 g of methacryloxy-γ-butyrolactone, and 3-hydroxy-1-gold. 2.08 g of an alkyl methacrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran as a reaction solution. The reaction solution was kept at 63 ° C under a nitrogen atmosphere, and allowed to polymerize for 22 hours, after which the reaction solution was dropped into 400 mL of n-hexane. The resulting resin thus obtained was solidified and purified, and the resulting white powder was filtered and dried under reduced pressure at 40 ° C overnight.

In the above formula (11), "40", "40", and "20" indicate the ratio of each constituent unit, and do not indicate a block copolymer.

Next, the photoresist layer was exposed using an electron beam drawing device (ELS-7500, 50 keV), and baked at 115 ° C for 90 seconds to obtain 2.38 mass % tetramethylammonium hydroxide ( The TMAH) aqueous solution was developed for 60 seconds, whereby a positive resist pattern was obtained.

The shape of the obtained resist pattern of 55 nmL/S (1:1) and 80 nmL/S (1:1) was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.

The shape of the developed resist pattern was evaluated, and the pattern was not collapsed, and the squareness was evaluated as "good", and the evaluation was "poor". Further, as a result of the above observation, the minimum line width in which the pattern is not collapsed and the squareness is good is used as an index for "resolution" evaluation. Furthermore, the minimum electron beam energy of a good pattern shape that can be depicted is used as an indicator of "sensitivity" evaluation.

The results of the evaluation are shown in Table 8.

 (Comparative Example 2)  

The same procedure as in Example 2 was carried out except that the formation of the underlayer film was not carried out, and the photoresist layer was directly formed on the SiO ₂ substrate to obtain a positive resist pattern. The results are shown in Table 8.

As can be understood from Table 8, it can be confirmed at least that Examples 1-1 to 2-2 using Al-BiN-1, Al-BiP-1, AlOH-BiN-1 or AlOH-BiP-1 are compared with Comparative Examples. 1. It is good at any point of heat resistance, solubility and etching resistance. On the other hand, Comparative Example 1 using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resin) was inferior in etching resistance.

Further, in Examples 38 to 41, it was confirmed that the shape of the resist pattern after development was good, and no defects were observed. In addition, in Comparative Example 2 in which the formation of the underlayer film was omitted, it was confirmed that it was intentionally excellent in both resolution and sensitivity.

Further, it was confirmed from the difference in the shape of the resist pattern after development that the underlayer film forming materials for lithography used in Examples 5 to 8 exhibited good adhesion to the resist material.

 <Examples 42 to 45>  

The solutions of the lithography underlayer film forming materials of Examples 1-1 to 2-2 were applied onto a SiO 2 substrate having a thickness of 300 nm, and baked at 240 ° C for 60 seconds and then at 400 ° C for 120 seconds. Thereby, a film having a film thickness of 80 nm or less is formed. On the underlayer film, a ruthenium-containing intermediate layer material was applied and baked at 200 ° C for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. Further, the resist solution for ArF was applied onto the interlayer film, and baked at 130 ° C for 60 seconds to form a photoresist layer having a film thickness of 150 nm. Further, in terms of the material containing the ruthenium intermediate layer, the ruthenium atom-containing polymer obtained below was used.

16.6 g of 3-carboxypropyltrimethoxydecane, 7.9 g of phenyltrimethoxydecane and 14.4 g of 3-hydroxypropyltrimethoxydecane were dissolved in 200 g of tetrahydrofuran (THF) and 100 g of pure water to adjust the temperature of the solution. After adjusting to 35 ° C, 5 g of oxalic acid was added dropwise, and then the temperature was raised to 80 ° C to carry out a condensation reaction of stanol. Next, 200 g of diethyl ether was added, the aqueous layer was separated, the organic layer was washed twice with ultrapure water, and 200 g of propylene glycol monomethyl ether acetate (PGMEA) was added thereto, and the liquid temperature was heated to 60 ° C. The THF was removed under reduced pressure to remove diethyl ether water to obtain a ruthenium-containing polymer.

Next, using a wire drawing apparatus (ELION-7500, 50 keV), the photoresist layer was exposed to a mask and baked (PEB) at 115 ° C for 90 seconds, and was 2.38 mass % tetramethylammonium. An aqueous solution of hydroxide (TMAH) was developed for 60 seconds to obtain a positive resist pattern of 55 nmL/s (1:1).

Thereafter, the obtained resist pattern was masked using RIE-10NR manufactured by SAMCO Co., Ltd., and a dry etching process was performed on the ruthenium containing interlayer film (SOG), and then the obtained ruthenium-containing interlayer film pattern was sequentially applied. The mask performs dry etching of the underlayer film, and the resulting underlying film pattern is masked to perform dry etching of the SiO ₂ film.

Various etching conditions are as follows.

Etching conditions of the resist interlayer film to the resist pattern

Output: 50W

Pressure: 20Pa

Time: 1min

Etching gas

Ar gas flow: CF ₄ gas flow: O ₂ gas flow = 50: 8: 2 (sccm)

Etching conditions of the underlayer film of the resist intermediate film pattern

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

Ar gas flow: CF ₄ gas flow: O ₂ gas flow = 50: 5: 5 (sccm)

Etching conditions of SiO ₂ film to the underlying film pattern

Output: 50W

Pressure: 20Pa

Time: 2min

Etching gas

Ar gas flow: C ₅ F ₁₂ gas flow: C ₂ F ₆ gas flow: O ₂ gas flow = 50: 4: 3: 1 (sccm)

 [Evaluation]  

The cross-section of the pattern (the shape of the SiO ₂ film after etching) obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., and it was found that the multilayer film was used as an example of the underlayer film of the present embodiment. The shape of the SiO ₂ film after the etching in the processing of the agent was a rectangle, and no defects were observed, which was confirmed to be good.

 [Examples 46 to 65]  

Using the respective compounds synthesized in the above Synthesis Examples and Synthesis Examples, the optical component forming compositions were prepared by blending as shown in Table 9 below. Further, among the components of the optical component forming composition in Table 9, the following agents were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.

‧ Acid generator: T-butyl diphenyl sulfonium nonafluoromethane sulfonate (DTDPI) manufactured by Midori Chemical Co., Ltd.

‧ Crosslinker: NIKALAC MX270 (NIKALAC), manufactured by Sanwa Chemical Co., Ltd.

Organic solvent: propylene glycol monomethyl ether acetate acetate (PGMEA)

The optical component forming composition in a uniform state was spin-coated on a clean tantalum wafer, and then prebaked (prebake: PB) in an oven at 110 ° C to form an optical component forming film having a thickness of 1 μm. A composition was formed for the prepared optical component, and when the film formation was good, it was evaluated as "A", and when the formed film was defective, it was evaluated as "C".

After the uniform optical component forming composition was spin-coated on the clean tantalum wafer, PB was performed in an oven at 110 ° C to form a film having a thickness of 1 μm. For this film, the refractive index (λ = 589.3 nm) at 25 ° C was measured by a multi-incident angle spectroscopic ellipsometer VASE manufactured by J.A. Woollam. The film to be prepared was evaluated as "A" when the refractive index was 1.6 or more, "B" when it was less than 1.55, and "C" when it was less than 1.55. When the transparency (λ = 632.8 nm) was 90% or more, the evaluation was "A", and when it was less than 90%, it was evaluated as "C".

 [Examples 50 to 71]  

Using the respective compounds synthesized in the above Synthesis Examples and Synthesis Examples, the resist compositions were prepared by blending as shown in Table 10 below. Further, among the components of the optical component forming composition in Table 10, the following agents were used for the acid generator, the crosslinking agent, the acid diffusion inhibitor, and the solvent.

‧Acid generator: Made from Chemical Corporation, Triphenylsulfonium Trifluoromethanesulfonate

‧ Crosslinking agent: NIKALAC MX270, manufactured by Sanwa Chemical Co., Ltd.

‧ Acid Diffusion Inhibitor: TDK, Tokyo Chemical Industry Co., Ltd.

‧Organic solvent: propylene glycol monomethyl ether (PGME) manufactured by Tokyo Chemical Industry Co., Ltd.

 [Evaluation method]    (1) Preservation stability and film formation of resist composition  

The storage stability of the resist composition was set to a resist composition, and then allowed to stand at 23 ° C and 50% RH for 3 days, and the presence or absence of precipitation was visually observed and evaluated. After standing for 3 days, if the resist composition was a uniform solution and there was no precipitation, it was evaluated as A, and if it was precipitated, it was evaluated as C. Further, after the resist composition in a uniform state was spin-coated on the cleaned silicon wafer, pre-exposure baking (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 40 nm. The resulting resist composition was evaluated as A when the film formation was good, and was evaluated as C when the formed film was defective.

 (2) Pattern evaluation of resist pattern  

After the uniform resist composition was spin-coated on the cleaned silicon wafer, pre-exposure baking (PB) was performed in an oven at 110 ° C to form a resist film having a thickness of 60 nm. For the obtained resist film, an electron beam drawing device (ELS-7500, manufactured by ELIONIX Co., Ltd.) was used to irradiate an electron beam having a line and pitch set at 1:1 intervals of 50 nm, 40 nm, and 30 nm. After the irradiation, the resist film was heated at a predetermined temperature for 90 seconds, and immersed in PGME for 60 seconds to perform development. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern. With respect to the formed resist pattern, the line and the pitch were observed by a scanning electron microscope (S-4800, Hitachi High-Tech Co., Ltd.), and the reactivity of the resist composition by electron beam irradiation was evaluated.

The sensitivity is expressed by the amount of the minimum energy per unit area necessary for obtaining the pattern, and is evaluated in accordance with the following.

A: When the pattern is not available at 50 μC/cm ²

C: A case where a pattern can be obtained at 50 μC/cm ² or more

The pattern formation was observed by SEM (Scanning Electron Microscope), and evaluated according to the following.

A: The case of getting a rectangular pattern

B: When the approximate rectangle pattern is obtained

C: When a non-rectangular pattern is obtained

As described above, the present invention is not limited to the above-described embodiments and examples, and may be appropriately modified without departing from the scope of the invention.

The compound of the present invention and the resin have high solubility in a safe solvent, and are excellent in heat resistance and etching resistance, and the resist composition of the present invention imparts a good resist pattern shape.

Further, a compound for forming a photoresist underlayer film which is excellent in heat resistance and etching resistance, a resin, and a film forming composition for lithography can be realized. Further, since the film forming composition for lithography uses a compound or resin having a specific structure having high heat resistance and high solvent solubility, deterioration of the film at the time of high-temperature baking can be suppressed, and oxygen plasma etching or the like can be performed. A resist and an underlayer film excellent in etching resistance. Further, when the underlayer film is formed, since the adhesion to the resist layer is also excellent, an excellent resist pattern can be formed.

Further, since the refractive index is high and the coloring can be suppressed by the low temperature to high temperature treatment, it can be used as a composition for various optical parts.

Therefore, the present invention can be used as an electrical laminate or electric device mounted on, for example, an electrical insulating material, a resist resin, a semiconductor encapsulating resin, an adhesive for a printed wiring board, an electric device, an electronic device, an industrial device, or the like. Matrix resin, build-up laminate material, fiber-reinforced plastic resin, resin for encapsulation of liquid crystal display panel, coating material, various coating agents, adhesives, and semiconductors for prepregs mounted on equipment, electronic equipment, industrial equipment, etc. A coating lens, a resin for a resist for a semiconductor, a resin for forming a lower film, a film, and a sheet, a plastic lens (a lens, a convex lens, a microlens, a Fresnel lens, and a viewing angle control) Lens, contrast lift lens, etc., retardation film, electromagnetic shielding film, germanium, optical fiber, solder resist for flexible printed wiring, plating resist, interlayer insulating film for multilayer printed wiring board, photosensitive optical waveguide, etc. Optical parts and the like can also be widely and effectively utilized.

The present application is based on Japanese Patent Application No. 2016-178443, filed on Jan.

 [Industrial availability]  

The present invention has industrial applicability in the field of lithographic resists, underlayer films for lithography, and underlayer films and optical parts for multilayer resists.

Claims (37)

a compound represented by the following formula (0), (In the formula (0), R ^Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z is an N-valent group or a single bond having 1 to 60 carbon atoms, and R ^{T is} independently An alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1 to 30 alkoxy group, halogen atom, nitro group, amine group, carboxylic acid group, thiol group or hydroxyl group, the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may contain an ether bond or a ketone bond Or an ester bond, wherein at least one of R ^T is a hydroxyl group, and at least one of R ^T is an alkenyl group having 2 to 30 carbon atoms, and X represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m each independently An integer of 0 to 9, where at least one of m is an integer of 2 to 9 or at least two of m are integers of 1 to 9, and N is an integer of 1 to 4, where N is an integer of 2 or more. The structural formulas of the N [ ] may be the same or different, and r are each independently an integer of 0 to 2). The compound of the formula (1), wherein the compound represented by the formula (0) is a compound represented by the following formula (1), (In the formula (1), R ⁰ is synonymous with the above R ^Y , R ¹ is an n-valent group or a single bond having 1 to 60 carbon atoms, and R ² to R ⁵ are each independently a carbon number which may have a substituent 1 An alkyl group of ~30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, and a halogen An atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may contain an ether bond, a keto bond or an ester bond, and here, R ² At least one of ~R ⁵ is a hydroxyl group, and at least one of R ² to R ⁵ is an alkenyl group having 2 to 30 carbon atoms, and m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently The ground is an integer of 0 to 9, except that m ² , m ³ , m ⁴ and m ^{5 are} not 0 at the same time, and at least one of m ² , m ³ , m ⁴ and m ⁵ is an integer of 2 to 8 or 2 to 9 Or at least two of m ² , m ³ , m ⁴ and m ⁵ are integers of 1 to 8 or 1 to 9, and n is synonymous with the above N. Here, when n is an integer of 2 or more, n [ ] The structural formulas may be the same or different, and p ² to p ⁵ are each independently synonymous with the aforementioned r). The compound of the formula (1), wherein the compound represented by the formula (0) is a compound represented by the following formula (2), (Formula 2) (, R ^0A line is synonymous with the R ^Y, R ^1A is n ^A carbon number of the monovalent group of 1 to 30, or a single bond, R ^2A each independently may have a substituent group of carbon number 1 to 30 An alkyl group, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may contain an ether bond, a keto bond or an ester bond, and here, at least R ^2A One is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms, and n ^A is synonymous with the above N. Here, when n ^A is an integer of 2 or more, n ^A of the structural formulas in [ ] The same or different, X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^2A are each independently an integer of 0-7, but at least one m ^2A is an integer of 2-7 or at least The two m ^2A are integers from 1 to 7, and q ^A are each independently 0 or 1). The compound of the formula (1), wherein the compound represented by the formula (1) is a compound represented by the following formula (1-1), (In the formula (1-1), R ⁰ , R ¹ , R ⁴ , R ⁵ , n, p ² to p ⁵ , m ⁴ and m ⁵ are synonymous with the above, and R ⁶ to R ⁷ are each independently capable of having The alkyl group having 1 to 30 carbon atoms of the substituent, the aryl group having 6 to 30 carbon atoms which may have a substituent, the alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, and a carboxyl group An acid group or a thiol group, wherein at least one of R ⁶ to R ⁷ is an alkenyl group having 2 to 30 carbon atoms, R ¹⁰ to R ¹¹ are each independently a hydrogen atom, and m ⁶ and m ⁷ are each independently 0. - an integer of 7, ^{but, m 4, m 5, m} 6 , and m ⁷ are not simultaneously 0). The compound of the formula (1-1), wherein the compound represented by the formula (1-1) is a compound represented by the following formula (1-2), (In the formula (1-2), R ⁰ , R ¹ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , n, p ² to p ⁵ , m ⁶ and m ⁷ are synonymous with the above, R ⁸ to R ⁹ It is synonymous with R ⁶ to R ⁷ described above, and R ¹² to R ¹³ are synonymous with R ¹⁰ to R ¹¹ described above, and m ⁸ and m ⁹ are each independently an integer of 0 to 8, but m ⁶ , m ⁷ , m ⁸ And m ^{9 is} not 0). The compound of the formula (2), wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1), (In the formula (2-1), R ^0A , R ^1A , n ^A , q ^A and X ^{A are the} same as defined above, and each of R ^{3A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms having a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein R ^3A At least one is an alkenyl group having 2 to 30 carbon atoms, and each of R ^{4A is} independently a hydrogen atom, and m ^{6A is} each independently an integer of 0 to 5).  A resin obtained by using the compound described in claim 1 as a monomer.   The resin as recited in claim 7, which has the structure shown by the following formula (3), (In the formula (3), L may have a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms of a substituent, and an extended aryl group having 6 to 30 carbon atoms which may have a substituent. The alkylene group having a carbon number of from 1 to 30 or a single bond, the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may contain an ether bond, a ketone bond or an ester bond, and the R ⁰ system is as described above. synonymous R ^Y, R ¹ is n-valent carbon number of 1 to 60, or a single bond, R ² ~ R ⁵ each independently may have a substituent group of a carbon number of an alkyl group having 1 to 30, may have a substituent group of carbon An aryl group of 6 to 30, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl group, the above alkenyl group and the alkoxy group may contain an ether bond, a keto bond or an ester bond, and here, at least one of R ² to R ⁵ is a hydroxyl group, and R ² At least one of ~R ⁵ is an alkenyl group having 2 to 30 carbon atoms, m ² and m ³ are each independently an integer of 0 to 8, and m ⁴ and m ⁵ are each independently an integer of 0 to 9, except m ² , m ^3, m ⁴ and m ⁵ are not simultaneously 0, m ^2, m ^3, at least a 2 to 8 or 2 to 9 of the m ⁴ and m ⁵ Number or m ^2, m ^3, m ⁴ and m ⁵ is an integer of at least two of 1 to 8 or 1 to 9 of). The resin as recited in claim 7, which has the structure shown by the following formula (4), (In the formula (4), L is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^0A is synonymous with the above R ^Y , and R ^1A is a carbon number of 1 to 30 n ^A The valence group or a single bond, each of R ^{2A is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 2 An alkenyl group of 30, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, the aforementioned aryl group, and the aforementioned alkenyl group And the alkoxy group may comprise an ether bond, a ketone bond or an ester bond, wherein at least one of R ^2A is a hydroxyl group, and at least one of R ^2A is an alkenyl group having 2 to 30 carbon atoms, and n ^A is synonymous with the aforementioned N Here, when n ^A is an integer of 2 or more, the structural formulas of n ^A of [ ] may be the same or different, and X ^A represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^{2A is} independent of each other. The ground is an integer from 0 to 7, except that at least one of m ^2A is an integer of 2 to 7 or at least two of m ^2A are integers of 1 to 7, and q ^{A is} independently 0 or 1). a compound represented by the following formula (0-A), (In the formula (0-A), R ^Y' is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R ^Z' is an N-valent group or a single bond having 1 to 60 carbon atoms, R Each of ^{T' is} independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and may have The alkoxy group having 1 to 30 carbon atoms of the substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the alkoxy group may include An ether bond, a ketone bond or an ester bond, wherein at least one of R ^{T '} is an alkenyloxy group having 2 to 30 carbon atoms, and X' represents an oxygen atom, a sulfur atom, a single bond or no crosslink, and m' is independently The ground is an integer from 0 to 9, where at least one of m' is an integer from 1 to 9, and N' is an integer from 1 to 4. Here, when N' is an integer of 2 or more, N' is [ ] The structural formulas in the middle may be the same or different, and r' are each independently an integer of 0 to 2). The compound of the formula (0-A), wherein the compound represented by the formula (0-A) is a compound represented by the following formula (1-A), (In the formula (1-A), R ^{0 '} is synonymous with the above R ^{Y '} , R ^{1 '} is an n-valent group or a single bond having a carbon number of 1 to 60, and R ^{2 '} to R ^{5 '} are each independently independently An alkyl group having 1 to 30 carbon atoms having a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and a carbon number which may have a substituent 1~ Alkoxy group of 30, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may contain an ether bond, a ketone bond or an ester a bond, wherein at least one of R ^{2 '} to R ^{5 '} is an alkenyloxy group having 2 to 30 carbon atoms, and m ^{2 '} and m ^{3 '} are each independently an integer of 0 to 8, m ^{4 '} and m ^{5 'They} are independently integers from 0 to 9, except that m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0 at the same time, and n ' is synonymous with the above N', where n' is 2 or more. In the case of an integer, the structural formulas in n' of [ ] may be the same or different, and p ^{2 '} ~ p ^{5 '} is synonymous with the aforementioned r). The compound of the formula (0-A), wherein the compound represented by the formula (0-A) is a compound represented by the following formula (2-A), (In the formula (2-A), R ^{0A '} is synonymous with the above R ^{Y '} , R ^{1A '} is a n ^A valent group or a single bond having a carbon number of 1 to 30, and R ^{2A ' is} each independently a substituent. An alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and an alkyl group having 1 to 30 carbon atoms which may have a substituent An oxy group, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aforementioned alkyl group, the aforementioned aryl group, the aforementioned alkenyl group and the aforementioned alkoxy group may contain an ether bond, a ketone bond or an ester bond. Here, at least one of R ^2A′ is an alkenyloxy group having 2 to 30 carbon atoms, and n ^A′ is synonymous with the above N. Here, when n ^A′ is an integer of 2 or more, n ^A′ of [ ] The structural formula may be the same or different, X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no cross-linking, and m ^2A' are each independently an integer of 0-7, but at least one m ^2A' is 1 An integer of ~7, q ^{A' is} independently 0 or 1). The compound of the formula (1-A), wherein the compound represented by the formula (1-A) is a compound represented by the following formula (1-1-A), (In the formula (1-1-A), R ^0' , R ^{1 '} , R ^{4 '} , R ^{5 '} , n, p ^{2 '} to p ^{5 '} , m ^{4 '} and m ^{5 '} are synonymous with the above, R ^6' to R ^7' are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an alkyl group having 2 to 30 carbon atoms which may have a substituent a group, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group, wherein R ^{10 '} to R ^{11 '} are each independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms, here, R ¹⁰ At least one of ^' ~R ^{11 '} is an alkenyl group having 2 to 30 carbon atoms, and m ^{6 '} and m ^{7 '} are each independently an integer of 0 to 7, except m ^{4 '} , m ^{5 '} , m ^{6 '} and m ^{7' is} not 0 at the same time. The compound of the formula (1-1-A), wherein the compound represented by the formula (1-1-A) is a compound represented by the following formula (1-2-A), (In the formula (1-2-A), R ^0' , R ^{1 '} , R ^6' , R ^7' , R ^{10 '} , R ^{11 '} , n ', p ^{2 '} ~ p ^{5 '} , m ^{6 '} and m ^{7 '} is synonymous with the above, R ^{8 '} ~ R ^{9 '} is synonymous with R ^{6 '} ~ R ^{7 '} , R ^{12 '} ~ R ^{13 '} is synonymous with R ^{10 '} ~ R ^{11 '} , m ^{8 '} and m ^{9 'is} independently an integer from 0 to 8, except that m ^{6 '} , m ^{7 '} , m ^{8 '} and m ^{9 ' are} not 0). The compound of the formula (2-A), wherein the compound represented by the formula (2-A) is a compound represented by the following formula (2-1-A), (In the formula (2-1-A), R ^0A' , R ^1A' , n ^A' , q ^A' and X ^{A' are the} same as defined above, and R ^3A' are each independently a carbon number which may have a substituent An alkyl group of 1 to 30, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group or a thiol group Further, each of R ^{4A' is} independently a hydrogen atom or an alkenyl group having 2 to 30 carbon atoms. Here, at least one of R ^4A' is an alkenyl group having 2 to 30 carbon atoms, and m ^{6A' is} independently An integer from 0 to 5.)  A resin obtained by using the compound described in claim 10 as a monomer.   The resin as recited in claim 16 has the structure shown by the following formula (3-A). (In the formula (3-A), the L system may have a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms of a substituent, and a carbon number of 6 to 30 which may have a substituent. a substituent having an alkylene group or a single bond having 1 to 30 carbon atoms, the alkylene group, the above-mentioned extended aryl group and the aforementioned alkoxy group may contain an ether bond, a keto bond or an ester bond, and R ^0' It is synonymous with the above R ^{Y '} , R ^{1 '} is an n-valent group or a single bond having a carbon number of 1 to 60, and R ^{2 '} to R ^{5 '} are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent. An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, An amino group, a carboxylic acid group, a thiol group or a hydroxyl group, the alkyl group, the aryl group, the aforementioned alkenyl group and the alkoxy group may contain an ether bond, a keto bond or an ester bond, and here, R ^{2 '} to R ^5' At least one of the alkenyloxy groups having a carbon number of 2 to 30, m ^{2 '} and m ^{3 '} are each independently an integer of 0 to 8, and m ^{4 '} and m ^{5 '} are each independently an integer of 0 to 9, except , m ^{2 '} , m ^{3 '} , m ^{4 '} and m ^{5 ' are} not 0) at the same time. The resin as recited in claim 16, which has the structure shown by the following formula (4-A), (In the formula (4-A), L' is a linear or branched alkyl or single bond having a carbon number of 1 to 30, R ^0A' is synonymous with the above R ^{Y '} , and R ^1A' is a carbon number. 1 to 30 of the n-valent group ^a or a single bond, R ^{2A 'each} independently may have a substituent group of carbon number of alkyl group of 1 to 30, may have a substituent group of carbon number of the aryl group having 6 to 30, may have a The alkenyl group having 2 to 30 carbon atoms of the substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amine group, a carboxylic acid group, a thiol group or a hydroxyl group, the aforementioned alkyl group, The aryl group, the aforementioned alkenyl group and the alkoxy group may include an ether bond, a ketone bond or an ester bond, and here, at least one of R ^2A′ is an alkenyloxy group having 2 to 30 carbon atoms, and the n ^A′ system is as described above. N is synonymous. Here, when n ^A' is an integer of 2 or more, the structural formulas of [ ] in n ^{A '} may be the same or different, and X ^{A '} represents an oxygen atom, a sulfur atom, a single bond or no crosslinking. , m ^2A' are each independently an integer from 0 to 7, except that at least one of m ^2A' is an integer from 1 to 7, and q ^{A' is} independently 0 or 1).  A composition comprising the compound according to any one of claims 1 to 6 and the resin according to any one of claims 7 to 9, and the compound according to any one of claims 10 to 15 and the request One or more selected from the group consisting of the resins described in any one of Items 16 to 18.    The composition according to claim 19, which further contains a solvent.    The composition according to claim 19 or 20, which further contains an acid generator.    The composition according to any one of claims 19 to 21, which further comprises a crosslinking agent.    The composition according to claim 22, wherein the crosslinking agent is a phenol compound, an epoxy compound, a cyanate compound, an amine compound, a benzoxazine compound, a melamine compound, a guanamine compound, or an acetylene urea compound. At least one selected from the group consisting of a urea compound, an isocyanate compound, and an azide compound.    The composition according to claim 22, wherein the crosslinking agent has at least one allyl group.    The composition according to claim 22, wherein the content of the crosslinking agent is 0.1 to 50% by mass based on the total mass of the solid component.    The composition according to claim 22, which further contains a crosslinking accelerator.    The composition according to claim 26, wherein the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.    The composition according to claim 26, wherein the content of the crosslinking accelerator is 0.1 to 5% by mass based on the total mass of the solid component.    The composition according to any one of claims 19 to 21, which further comprises a radical polymerization initiator.    The composition according to any one of claims 19 to 21, wherein the radical polymerization initiator is a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator. At least one selected from the group.    The composition according to any one of claims 19 to 21, wherein the content of the radical polymerization initiator is 0.05 to 25% by mass based on the total mass of the solid component.    The composition according to any one of claims 19 to 21, which is used for the formation of a film for lithography.    The composition according to any one of claims 19 to 21, which is used for the formation of a resist permanent film.    The composition according to any one of claims 19 to 21, which is used for the formation of an optical component.    A resist pattern forming method comprising the steps of: forming a photoresist layer on a substrate using the composition described in claim 32, irradiating a predetermined region of the photoresist layer with radiation, and performing development .    A resist pattern forming method comprising the steps of: forming an underlayer film on a substrate using the composition described in claim 32, and forming at least one photoresist layer on the underlayer film, A predetermined area of the photoresist layer is irradiated with radiation to perform development.    A circuit pattern forming method comprising the steps of: forming an underlayer film on a substrate using the composition described in claim 32, and forming an interlayer film on the underlying film using a resist interlayer film material, in the middle a step of forming at least one photoresist layer on the film, irradiating radiation to a predetermined region of the photoresist layer, performing a process to form a resist pattern, and etching the resist pattern as a mask In the interlayer film, the obtained interlayer film pattern is used as an etching mask to etch the underlayer film, and the obtained underlayer film pattern is used as an etching mask etching substrate, thereby forming a pattern on the substrate.