TWI573819B - Silicone skeleton-containing polymer compound and method for producing same, chemically amplified negative resist composition, photo-curable dry film and method for producing same, patterning process, layered product, and substrate - Google Patents

Description

Polymer compound containing polyxanylene skeleton, method for producing the same, chemically amplified negative photoresist material, photocurable dry film, method for producing the same, pattern forming method, laminate, and substrate

The present invention relates to a polymer compound containing a polyfluorene skeleton, a method for producing the same, a chemically amplified negative photoresist material using the polymer compound containing a polyfluorene skeleton, and a chemically amplified negative photoresist material. a photocurable dry film, a method for producing the same, a pattern forming method using the above chemically amplified negative resist material or the photocurable dry film, and a laminate obtained by laminating the photocurable dry film on a substrate And a substrate obtained by the above pattern forming method.

With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and mobile phones, the demand for smaller, thinner, and higher-density semiconductor devices has been rapidly increasing. Therefore, it is desired to develop an increase in the substrate area that can be improved in productivity, and a high-density packaging technology such as a wafer size package or a wafer level package (CSP) or a three-dimensional laminate can be made to be fine on the substrate. A photosensitive insulating material of a structure having a high aspect ratio and a high unevenness.

As the photosensitive insulating material as described above, it has been proposed to provide a wide range of film thicknesses by spin coating which is commonly used in a semiconductor device manufacturing step, and to form fine patterns in a wide range of wavelength regions, which can be provided by hardening after low temperature. A photocurable resin composition of a film for electrical and electronic component protection which is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance (Patent Document 1). This spin coating method has the advantage of being able to form a film easily on a substrate.

On the other hand, the photocurable resin composition for providing a film for electrical and electronic component protection is used on a substrate to have a film thickness of 1 to 100 μm, but the viscosity of the photocurable resin composition is from a film thickness of about 30 μm. It becomes very high, and it is practically difficult to form a film on a substrate by spin coating.

Further, when the photocurable resin composition is applied to a substrate having irregularities on its surface by a spin coating method, it is difficult to substantially uniformly coat the substrate. Therefore, the gap between the photocurable resin layers tends to occur in the height difference portion of the substrate, and the flatness and the level difference coverage are further improved. Further, as another coating method instead of the spin coating method, a spraying method has been proposed (Patent Document 2). However, in principle, there is a problem that the height difference of the unevenness of the substrate or the pinhole of the film at the edge of the pattern and the pinhole of the bottom surface of the concave portion are likely to occur, and the problem of flatness and high and low coverage is not sufficiently solved.

Moreover, in recent years, high-density packaging technologies such as wafer-sized packages or wafer-level packages (CSP) or three-dimensional laminates have been actively implemented to form fine and high aspect ratio patterns on substrates, and to obtain pattern laminates. A metal such as copper is a technique of applying rewiring from a wafer. With the increase in density and high integration of the wafer, the pattern line width of the rewiring technology and the size of the contact hole between the connection substrates are extremely demanding. The method of obtaining a fine pattern is generally a lithography technique in which a chemically amplified negative-type photoresist material is suitable for obtaining a fine pattern. In addition, the pattern used for rewiring is characterized by permanent presence of device wafers and inter-wafer curing, and electrical and electronic parts protection that is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance. The film is used, so that the photoresist material that obtains the pattern is suitable for the negative type.

As described above, in order to form a material for re-wiring and patterning, and to form a film for electrical and electronic parts protection which is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance, chemical growth is performed. Type negative photoresist materials are suitable.

On the other hand, a chemically amplified negative-type photoresist material which can form a fine pattern in rewiring processing and is useful for electrical and electronic component protection coatings may be coated on a copper wiring or a coated substrate which is pre-processed on a substrate. Aluminum electrode. Further, the substrate on which the wiring and the electrode have been applied is also an insulating substrate such as tantalum nitride, and this tantalum nitride substrate is also required to be widely covered. However, the adhesion between the coating layer of the chemically amplified negative-type photoresist material and the substrates is insufficient, and the problem that the coating layer of the photoresist material peels off from the substrate often occurs.

On the other hand, when patterning is performed using a chemically amplified negative-type photoresist material useful for a film for electrical and electronic component protection, the developer used for development is often an organic solvent. The exposed portion is insoluble in the organic solvent of the developer due to the crosslinking reaction or the like, and the unexposed portion is well dissolved in the organic solvent of the developer to obtain a pattern.

However, the development of the organic solvent tends to be unfavorable when considering the treatment of the waste liquid after development, the load on the environment, and the like. Further, since the organic solvent developer is expensive, it is preferably developed by an alkali aqueous solution such as a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution which is inexpensively patterned and widely used.

When developing with an aqueous alkali solution such as 2.38% aqueous solution of TMAH, some negative-type photoresist materials used in recent years may occur: the difference in solubility between the exposed portion and the unexposed portion to the developer is small, that is, the difference in so-called dissolution contrast is small. When the dissolution contrast is small, it may not be expected to form a favorable pattern for forming a fine pattern. Further, when the dissolution contrast is small, there is a possibility that the pattern used for the exposure and transfer of the pattern is formed, and the pattern cannot be faithfully formed on the substrate. Therefore, it is desirable to have a developing solution using an aqueous alkali solution to obtain a large dissolution contrast ratio, that is, a photoresist having improved resolution.

In addition, it is important that a chemically amplified negative-type photoresist material which can form a fine pattern and is used for a film for electrical and electronic component protection during wiring processing is sufficiently dissolved in an alkali aqueous solution of a developing solution in an unexposed portion. That is, when the unexposed portion lacks solubility to the aqueous solution of the developer, when the photoresist is thick on the substrate, etc., there are dissolved residues, dross, and both sides of the pattern on the substrate. The pattern is degraded. In the steps of applying rewiring, such dross and tailing may cause defects such as electrical circuits and wiring breakage, and it is necessary to suppress the occurrence thereof.

Therefore, with the increase in the density and the high integration of the wafer, it is desirable to have a chemically amplified negative-type photoresist material that can be used for re-wiring technology to refine the pattern and to protect the film for electric and electronic parts protection, and it is desirable to have adhesion on the substrate. Significantly improved, it can be patterned with a developing solution of a general aqueous alkali solution such as 2.38% TMAH aqueous solution, and the resolution performance is expected to be improved, and it is desirable to construct a system without tailing and dross at the bottom of the pattern as soon as possible. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2008-184571 [Patent Document 2] JP-A-2009-200315

(The subject to be solved by the invention)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a problem of improving peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, and using a general-purpose 2.38% TMAH aqueous solution as a solution. a polymer compound containing a polyfluorene skeleton which is suitable for use as a base resin of a chemically amplified negative-type photoresist material which forms a fine pattern on the bottom of the pattern and on the substrate without dross or tailing, and a method for producing the same, and a method for producing the same A chemically amplified negative-type photoresist material containing a polymer compound of a polyoxyn skeleton is used. Still another object is to provide a method of simply applying the chemically amplified negative-type photoresist material to a substrate by spin coating to form a fine pattern. In addition, another object of the invention is to provide a photocurable dry film using the above-described chemically amplified negative-type photoresist material, a method for producing the same, and a laminate obtained by laminating the photocurable dry film on a substrate, On the substrate having irregularities, a method of applying a photoresist layer having a wide film thickness to form a fine pattern by using the above-mentioned photocurable dry film can also be used. Still another object is to provide a substrate in which the pattern obtained by the above-described pattern forming method is used for curing by a hardened film obtained by post-hardening at a low temperature. (method of solving the problem)

In order to solve the above problems, the present invention provides a polymer compound containing a polyfluorene skeleton having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 3,000 to 500,000. 【化1】 (wherein R ¹ to R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be different or identical to each other. m is an integer of 1 to 100. a, b, c, d, e, and f are 0 or A positive number, g and h are positive numbers, but a+b+c+d+e+f+g+h=1. Further, X is a divalent organic group represented by the following formula (2), and Y is a divalent organic group represented by the following formula (3), and W is the following The divalent organic group represented by the formula (4), and U is a divalent organic group represented by the following formula (5).) [Chemical 2] (wherein Z is selected from the divalent organic group of any one of the following) The dotted line represents the bond and n is 0 or 1. R ⁵ and R ^{6 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. x is any one of 0, 1, and 2. ) 【化4】 (wherein V is selected from the divalent organic group of any one of the following) The dotted line represents the bond and p is 0 or 1. R ⁷ and R ^{8 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. y is any of 0, 1, and 2. ) 【化6】 (wherein, the dotted line represents a bond, T represents an alkyl group having a carbon number of 1 to 10 or a divalent aromatic group, and R ⁹ represents a hydrogen atom or a methyl group.) (wherein, the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group.)

If such a polymer compound containing a polyfluorene skeleton is used, the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, can be improved, and it can be used as a general purpose. 2.38% TMAH aqueous solution is a developing solution, and a base resin of a chemically amplified negative-type photoresist material which forms a fine pattern on the bottom of the pattern and on the substrate without slag or tailing.

In this case, R ¹⁰ in the above formula (5) is preferably a monovalent carboxyl group-containing organic group represented by the following formula (6). 【化8】 (wherein, the dotted line represents a bond, and R ¹¹ to R ¹⁴ are each a different or the same substituent, and represent a hydrogen atom, a halogen atom, a linear, branched, cyclic alkyl group having a carbon number of 1 to 12, The aromatic group, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may each be bonded to form a substituted or unsubstituted cyclic structure having 1 to 12 carbon atoms. j is any one of 1 to 7.

If it is such a polymer compound containing a polyoxygen skeleton, the effect of the present invention can be further improved.

At this time, a in the above formula (1) is 0≦a≦0.5, b is 0≦b≦0.3, c is 0≦c≦0.5, d is 0≦d≦0.3, and e is 0≦e≦0.8, f is 0≦f≦0.5, g is 0<g≦0.8, and h is 0<h≦0.5.

If it is such a polymer compound containing a polysiloxane skeleton, the effect of the present invention can be further improved.

At this time, a in the above formula (1) is a=0, b is b=0, c is c=0, d is d=0, e is 0≦e≦0.3, and f is 0≦f≦0.2, g is 0 < g ≦ 0.8, and h is 0 < h ≦ 0.5 is preferred.

If it is such a polymer compound containing a polysiloxane skeleton, the effect of the present invention can be further improved.

Furthermore, the present invention provides a method for producing a polymer compound containing a polyfluorene skeleton, which is an alcohol or phenol having a polymer compound having a polyfluorene skeleton and having a repeating unit represented by the following formula (7) All or a part of the hydroxyl group is reacted with a dicarboxylic anhydride to introduce a carboxyl group. 【化9】 (wherein R ¹ to R ⁴ , a, b, c, d, m, X, Y, and W are the same as described above. k and l are positive numbers and k=e+g, l=f+h. Further, e, f, g, and h are the same as before.)

In order to obtain the above-mentioned polymer compound containing a polyfluorene skeleton, such a production method is suitable.

In this case, the polymer compound containing a polyfluorene skeleton represented by the above formula (7) is preferably a hydrosilylene represented by the following structural formula (8) and a dihydrogen organic compound represented by the following formula (9). Any one or both of oxoxanes, a phenol compound having two allyl groups represented by the following formula (10), and a compound having two allylic groups represented by the following formula (11) Or both, and a phenol compound having two allyl groups represented by the following formula (12), preferably obtained by polymerization in the presence of a catalyst; 【化11】 (wherein R ³ , R ⁴ , and m are the same as defined above.) (wherein Z, R ⁵ , R ⁶ , n, and x are the same as described above.) [Chem. 13] (wherein, V, R ⁷ , R ⁸ , p, and y are the same as described above.) [Chem. 14] (wherein T and R ^{9 are the} same as above.).

In order to obtain the above-mentioned polymer compound containing a polyfluorene skeleton, such a production method is more suitable.

In this case, it is preferred to use a compound represented by the following formula (13) as the phenol compound having two allyl groups represented by the above formula (12). 【化15】 (wherein R ^{9 is the} same as above, and s is a positive number from 1 to 12.)

In order to obtain the above polymer compound having a polyoxymethylene skeleton having an alcoholic hydroxyl group, such a compound is suitable.

In this case, it is preferred to use a compound represented by the following formula (14) as the phenol compound having two allyl groups represented by the above formula (12). 【化16】 (wherein R ^{9 is the} same as above.)

In order to obtain the above-mentioned polymer compound containing a polyoxymethylene skeleton having a phenolic hydroxyl group, such a compound is suitable.

Further, the present invention provides a polymer compound containing a polyfluorene skeleton having a repeating unit represented by the following formula (24) and having a weight average molecular weight of 3,000 to 500,000. 【化1】 (In the formula, R ²¹ to R ²⁴ may be different or the same, and may represent a monovalent organic group having 1 to 15 carbon atoms, and may also contain an oxygen atom. R ¹⁸ and R ¹⁹ may be different or the same, and represent a carbon number of 1 The monovalent organic group of ~28 may also contain an oxygen atom. m' is an integer from 0 to 100, and o is an integer from 0 to 100. c', d', e', and f' are 0 or a positive number, a', b', g' and h' are positive numbers. Only a'+b'+c'+d'+e'+f'+g'+h'=1. Further, X' is represented by the following general formula (25) or general formula (26) a divalent organic group, Y is a divalent organic group represented by the following formula (3), W is a divalent organic group represented by the following formula (4), and U is a divalent value represented by the following formula (5) Organic base.) 【化18】 (The broken line represents a bond, and each of R ⁵ and R ⁶ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different from each other. x is any one of 0, 1, and 2.) 19] (wherein V is a divalent organic group selected from any one of the following, [Chemical 20] The dashed line represents the bond and p is 0 or 1. R ⁷ and R ^{8 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. y is any of 0, 1, and 2. ) 【化21】 (wherein, the dotted line represents a bond, T represents an alkyl group having a carbon number of 1 to 10 or a divalent aromatic group, and R ⁹ represents a hydrogen atom or a methyl group.) (wherein, the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group.)

If such a polymer compound containing a polyfluorene skeleton is used, the problem of peeling on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, can be improved, and 2.38% of general use can be used. The TMAH aqueous solution forms a fine pattern on the substrate at the bottom of the pattern and on the substrate without slag or tailing, and it becomes the basis of the chemically amplified negative-type photoresist material having excellent mechanical strength, chemical resistance, reliability, and the like. Resin.

In the above formula (24), o is an integer of from 1 to 100, and R ²¹ to R ²⁴ may be the same or different, and are a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ is represented by the following formula (27). a phenyl substituent having a hydroxyl group or an alkoxy group, and R ¹⁹ and R ²¹ to R ²⁴ may be the same or different, and may be a monovalent organic group having 1 to 10 carbon atoms which may also contain an oxygen atom, or may be the same as R ¹⁸ . Or a phenyl substituent having a hydroxyl group or an alkoxy group represented by the following formula (27) is preferred. 【化23】 (wherein, r is an integer of 0 to 10, and R ²⁰ is a hydroxyl group or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms.)

In the case of using such a chemically amplified negative-type photoresist material containing a polymer compound having a polyfluorene skeleton, the crosslinking reactivity of the exposed portion can be improved at the time of pattern formation. Moreover, the crosslinking reactivity of the exposed portion is improved, the solubility of the exposed portion to the developer is reduced, and the dissolution contrast is increased.

In this case, the phenyl substituent represented by the above formula (27) is preferably one or two or more selected from the group consisting of the following formula (28). 【化24】 (In the formula, the straight line accompanying the wavy line represents the bonding hand.)

In the case of using such a chemically amplified negative-type photoresist material containing a polymer compound having a polyfluorene skeleton, the pattern formation can further improve the crosslinking reactivity of the exposed portion. Moreover, by further improving the crosslinking reactivity of the exposed portion, the solubility of the exposed portion to the developer is further reduced, and the dissolution contrast is increased.

Furthermore, the present invention provides a chemically amplified negative-type photoresist material comprising the following components: (A) the above-mentioned polymer compound containing a polyfluorene skeleton; (B) decomposing and generating light by a wavelength of 190 to 500 nm An acid photoacid generator; (C) a crosslinking agent selected from the group consisting of an amine condensate modified with formaldehyde or formaldehyde-alcohol, and an average of two or more methylol groups or alkoxylated groups in one molecule. a compound obtained by substituting a methyl phenol compound and a hydrogen atom of a hydroxyl group of a polyhydric phenol with an epoxy propyl group, and a hydrogen atom of a hydroxyl group of a polyhydric phenol, and a compound represented by the following formula (C-1) And one or more of two or more compounds having a nitrogen atom of a glycidyl group represented by the following formula (C-2); (wherein, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and z represents 1 or 2.) (D) solvent; and (E) basic Compound.

If such a chemically amplified negative-type photoresist material can improve the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly on a substrate such as tantalum nitride, a general-purpose 2.38% TMAH can be used. The aqueous solution is formed in a developing solution to form a fine pattern on the bottom of the pattern and on the substrate without dross or tailing.

Furthermore, the present invention provides a photocurable dry film having a structure in which a photocurable resin layer having a thickness of 10 to 100 μm is sandwiched between a support film and a protective film, and the photocurable resin layer is as described above. A chemically amplified negative photoresist material is formed.

In the case of such a photocurable dry film, a fine pattern can be formed in a wide range of film thicknesses and wavelength regions, and after curing at a low temperature, flexibility, heat resistance, electrical properties, adhesion, reliability, and drug resistance can be obtained. Excellent.

Furthermore, the present invention provides a method for producing a photocurable dry film, comprising the steps of: (I) continuously applying the chemically amplified negative photoresist material to a support film, and forming a photocurable resin layer; (II) The photocurable resin layer is continuously dried; (III) Further, a protective film is bonded to the photocurable resin layer.

In order to obtain the aforementioned photocurable dry film, such a production method is suitable.

Furthermore, the present invention provides a pattern forming method comprising the steps of: (1) applying the aforementioned chemically amplified negative-type photoresist material on a substrate and forming a photosensitive material film; (2) secondly, separating after heat treatment The photomask exposes the photosensitive material film with a high-energy ray or an electron beam having a wavelength of 190 to 500 nm; (3) development is performed using a developing solution after the heat treatment.

If such a pattern forming method is used, the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, can be improved, and a general-purpose 2.38% TMAH aqueous solution can be used in the developing solution. A fine pattern is formed on the bottom of the pattern and on the substrate without dross or tailing. Further, the application of the chemically amplified negative photoresist material can be carried out by a spin coating method.

Furthermore, the present invention provides a pattern forming method comprising the steps of: (i) adhering a photocurable resin layer exposed by peeling the protective film from the photocurable dry film to a substrate; (ii) Intercepting the support film or the support film in a state in which the support film is exposed to the photocurable resin layer by a high-energy ray or an electron beam having a wavelength of 190 to 500 nm; (iii) performing heat treatment after exposure; (iv) Development with a developing solution.

If such a pattern forming method is used, the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, can be improved, and a general-purpose 2.38% TMAH aqueous solution can be used in the developing solution. A fine pattern is formed on the bottom of the pattern and on the substrate without dross or tailing.

After the development step at this time, it is preferable to include a step of post-curing the film patterned by the development at a temperature of 100 to 250 °C.

The hardened film obtained in this manner is excellent in flexibility, adhesion to a substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to a flux liquid, and such a hardened film is used as a semiconductor element of a protective film. Excellent reliability, especially to prevent cracking during temperature cycle test.

In this case, the substrate may be a substrate having one or both of a groove having a width of 10 to 100 μm and a depth of 10 to 120 μm and a hole.

As described above, according to the photocurable dry film of the present invention, a photoresist layer having a wide range of film thickness can be applied to a substrate having irregularities to form a fine pattern.

Furthermore, the present invention provides a laminate in which a photocurable resin of the photocurable dry film is laminated on a substrate having either or both of a groove having a width of 10 to 100 μm and a depth of 10 to 120 μm and a hole. Layered.

If such a laminate is sufficiently filled as described above, it can be a laminate having good properties.

Further, the present invention provides a substrate in which a pattern formed by the pattern forming method is protected by a cured film.

Such a substrate can be a substrate protected by a cured film excellent in flexibility, adhesion, heat resistance, electrical properties, mechanical strength, chemical resistance, reliability, and crack resistance. (Effect of the invention)

As described above, according to the present invention, it is possible to provide a chemically amplified negative-type photoresist material capable of greatly improving the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly on a substrate such as tantalum nitride. A polymer compound containing a polyfluorene skeleton which is suitably used for a base resin, a method for producing the same, and a chemically amplified negative-type photoresist material using the polymer compound containing a polyfluorene skeleton. Moreover, by using the chemically amplified negative-type photoresist material, fine patterns can be formed without slag and tailing in a wide range of wavelength regions, and the high-density and high integration of the wafer can be achieved in the rewiring technology. The pattern is refined. Further, the chemically amplified negative-type photoresist material can be developed by using an aqueous alkali solution such as a 2.38% TMAH aqueous solution, and can provide a photocurable dry film and a pattern forming method using the film. Further, by performing post-hardening of the pattern obtained by such a pattern forming method at low temperature, flexibility, adhesion, heat resistance, electrical properties, mechanical strength, chemical resistance, reliability, and crack resistance can be obtained. Excellent hardened film protection substrate.

As described above, there is a need to improve the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly a substrate such as tantalum nitride, and a general-purpose 2.38% TMAH aqueous solution can be used as a developing solution at the bottom of the pattern. a fine pattern is formed on the substrate without slag or tailing, and the cured film is a chemically amplified, negatively resistive material, and the base resin of the chemically amplified negative-type photoresist material is suitable for use. Polymer compound.

In order to achieve the above object, the inventors of the present invention have found that a phenol compound having two allyl groups represented by the following formula (12), a hydroquinone represented by the following structural formula (8), and the following formula (9) a dihydroorganoorganoxane, a phenol compound having two allyl groups represented by the following formula (10), and a compound having two allyl groups represented by the following formula (11), The polymerization reaction is carried out in the presence of a medium to obtain a polymer compound containing a polyoxymethylene skeleton containing an alcoholic hydroxyl group or a polymer compound containing a polyoxyxylene skeleton containing a phenolic hydroxyl group, and then the above polymer compound containing a polyfluorene skeleton All or a part of the alcoholic hydroxyl group or the phenolic hydroxyl group is reacted with a dicarboxylic acid anhydride, and a carboxyl group can be introduced into the polyfluorene skeleton to obtain a polymer compound containing a polyoxonium skeleton containing a carboxylic acid and a siloxane chain. The inventors of the present invention have found that a chemically amplified negative-type photoresist material comprising the following polymerizable compound containing a polyfluorene skeleton and containing the following (A) to (E) components can be used. The formation of a fine pattern can greatly improve the problem of peeling occurring on a metal wiring such as copper or aluminum, an electrode, or a substrate, particularly on a substrate such as tantalum nitride, and can greatly improve substrate adhesion. The present invention has been completed based on the findings of a film for electrical and electronic component protection which is excellent in a hardened film obtained by the above-described pattern forming method.

The invention is described in detail below, but the invention is not limited thereto.

The polymer compound containing a polyfluorene skeleton of the present invention has a repeating unit represented by the following formula (1) and has a weight average molecular weight of 3,000 to 500,000. 【化26】 (wherein R ¹ to R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be different or identical to each other. m is an integer of 1 to 100. a, b, c, d, e, and f are 0 or A positive number, g and h are positive numbers, but a+b+c+d+e+f+g+h=1. Further, X is a divalent organic group represented by the following formula (2), and Y is a divalent organic group represented by the following formula (3), and W is the following The divalent organic group represented by the formula (4), and U is a divalent organic group represented by the following formula (5).) [Chem. 27] (wherein Z is a divalent organic group selected from any one of the following: [28] The dotted line represents the bond and n is 0 or 1. R ⁵ and R ^{6 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. x is any one of 0, 1, and 2. ) 【化29】 (wherein V is a divalent organic group selected from any one of the following: [30] The dotted line represents the bond and p is 0 or 1. R ⁷ and R ^{8 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. y is any of 0, 1, and 2. ) 【化31】 (wherein, the dotted line represents a bond, T represents an alkyl group having a carbon number of 1 to 10 or a divalent aromatic group, and R ⁹ represents a hydrogen atom or a methyl group.) (wherein, the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group.)

R ¹ to R ⁴ in the above formula (1) represent different or identical monovalent hydrocarbon groups having 1 to 8 carbon atoms, and preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group or a cyclohexyl group; and a vinyl group; a linear, branched or cyclic alkenyl group such as a propenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenethyl group; .

Further, m is an integer of from 1 to 100, and preferably an integer of from 1 to 80, from the viewpoints of compatibility with a crosslinking agent and a photoacid generator described later, and photocurability. Further, in consideration of the adhesion, electrical characteristics, and reliability of the substrate, a, b, c, d, e, and f are 0 or a positive number, and g and h are positive numbers. Only a+b+c+d+e+f+g+h=1. In this case, a, b, c, d, e, f, g, and h are: 0≦a≦0.5, 0≦b≦0.3, 0≦c≦0.5, 0≦d≦0.3, 0≦e≦0.8 0 ≦ f ≦ 0.5, 0 < g ≦ 0.8, and 0 < h ≦ 0.5 is preferred. For the above a, b, c, d, e, f, g, and h, in particular: i.0≦a≦0.5, 0≦b≦0.3, 0≦c≦0.5, 0≦d≦0.3, 0≦e ≦0.8, 0≦f≦0.5, 0<g≦0.8, and 0<h≦0.5 ii.0≦a≦0.5, 0≦b≦0.3 and c=0, d=0, 0≦e≦0.8,0 ≦f≦0.5, 0<g≦0.8, and 0<h≦0.5 iii.a=0, b=0, 0≦c≦0.5, 0≦d≦0.3, 0≦e≦0.8, 0≦f≦0.5 , 0<g≦0.8, and 0<h≦0.5 iv.a=0, b=0, c=0, d=0, 0≦e≦0.3, 0≦f≦0.2, 0<g≦0.8, and 0 < h ≦ 0.5 va = 0, b = 0, c = 0, d = 0, e = 0, f = 0, 0 < g ≦ 0.8, and 0 < h ≦ 0.5 is suitable.

At this time, the ideal range of e is 0≦e≦0.8, and the more desirable range is 0≦e≦0.6, and the more desirable range is 0≦e≦0.3.

Further, the ideal range of f is 0 < f ≦ 0.5, more preferably 0 < f ≦ 0.3. When f is 0.5 or less, the alkali aqueous solution of the object of the present invention can be prevented from being used for patterning of a developer to develop a developer which is hardly soluble in an aqueous alkali solution. Further, when f is 0.5 or less, it is possible to prevent the film from being formed into a film which is remarkably deteriorated and to deteriorate the workability, or to form a photocurable structure having a structure in which the support film and the protective film are sandwiched, which is another object of the present invention. In the case of a dry film, the protective film cannot be peeled off and cannot be used as a photocurable dry film.

Further, the ideal range of g is 0 < g ≦ 0.8, more preferably 0.2 ≦ g ≦ 0.8. When g is 0.2 or more, the solubility in the developing solution of the aqueous alkali solution is not impaired, and a favorable pattern can be obtained. In other words, when g is 0.2 or more and the unexposed portion in which the negative pattern is formed has good solubility in the developer solution of the aqueous alkali solution, even if the thickness of the coating material on the substrate is thick, the pattern can be prevented from occurring. The bottom has dissolved residue, dross, and the pattern on the substrate has a trailing pattern on both sides. On the other hand, when g is 0.8 or less, the solubility in the developer of the aqueous alkali solution is appropriate, and the crosslinking reaction used to obtain the negative pattern does not become insolubilized, and the problem that the pattern cannot be obtained can be suppressed.

On the other hand, the ideal range of h is 0 < h ≦ 0.5, more preferably 0 < h ≦ 0.3.

Further, X in the above formula (1) is a divalent organic group represented by the following formula (2), Y is a divalent organic group represented by the following formula (3), and W is the following formula (4) The divalent organic group represented by U is a divalent organic group represented by the following formula (5). 【化33】 (wherein Z is selected from the divalent organic groups of any of the following: [34] The dotted line represents the bond and n is 0 or 1. R ⁵ and R ^{6 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. x is any one of 0, 1, and 2. ) 【化35】 (wherein V is selected from the divalent organic group of any of the following: [36] The dotted line represents the bond and p is 0 or 1. R ⁷ and R ^{8 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. y is any of 0, 1, and 2. ) 【化37】 (wherein, the dotted line represents a bond, T represents an alkyl group having a carbon number of 1 to 10 or a divalent aromatic group, and R ⁹ represents a hydrogen atom or a methyl group.) (wherein, the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group.)

Further, R ¹⁰ in the above formula (5) may represent a monovalent carboxyl group-containing organic group represented by the following formula (6). 【化39】 (wherein, the dotted line represents a bond, and R ¹¹ to R ¹⁴ are each a different or the same substituent, and represent a hydrogen atom, a halogen atom, a linear, branched, cyclic alkyl group having a carbon number of 1 to 12, In the aromatic group, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may each be bonded to each other to form a substituted or unsubstituted cyclic structure having 1 to 12 carbon atoms. j is any one of 1 to 7.

The weight average molecular weight of the polymer compound containing a polyfluorene skeleton of the present invention is obtained by using the compatibility and photocurability of a chemically amplified negative-type photoresist material described later, and by a chemically amplified negative-type photoresist material. The viewpoint of the mechanical properties of the cured product is 3,000 to 500,000, preferably 5,000 to 300,000. Further, in the present invention, the weight average molecular weight is a polystyrene-converted oxime obtained by gel permeation chromatography (GPC).

Further, the present invention provides a method for producing the above-described polymer compound containing a polyfluorene skeleton according to the present invention. The method for producing a polymer compound containing a polyfluorene skeleton according to the present invention is a method for producing all or a part of an alcoholic or phenolic hydroxyl group of a polymer compound containing a polyfluorene skeleton having a repeating unit represented by the following formula (7). The dicarboxylic anhydride is reacted to introduce a carboxyl group. Further, in the method for producing a polymer compound containing a polyfluorene skeleton according to the present invention, a polymer compound having a polyfluorene skeleton having a repeating unit represented by the following formula (7) can be used as an intermediate material. 【化40】 (wherein R ¹ to R ⁴ , a, b, c, d, m, X, Y, and W are the same as described above. k and l are positive numbers and k=e+g, l=f+h. Further, e, f, g, and h are the same as before.)

In addition, the weight average molecular weight of the polymer compound containing a polyfluorene skeleton having a repeating unit represented by the above formula (7) which is an intermediate material is low, and the average molecular weight of the polymer compound containing the polyfluorene skeleton is also desired. Low, the viscosity of the target chemically amplified negative photoresist material is reduced. Therefore, the viscosity of the resin layer formed by using the chemically amplified negative-type photoresist material containing the polymer compound of the polyfluorene skeleton described above is also lowered. Further, in the molecule of the polymer compound containing a polyfluorene skeleton, the ratio of the molecular unit containing the linear polyoxane (when b, d, f, and h in the above formula (1) is increased, relative The ratio of the molecular units of the aromatic compound such as silphenylene (a, c, e, and g in the above formula (1) is decreased, and the viscosity of the polymer compound containing the polyfluorene skeleton is lowered. . Therefore, the viscosity of the resin layer formed by using the chemically amplified negative-type photoresist material containing the polymer compound of the polyfluorene skeleton described above is also lowered. Further, if the molecular chain length of the linear polyoxyalkylene in the molecule of the polymer compound containing the polyoxyn skeleton is increased, that is, the enthalpy of m of the above formula (1) is increased, and the above-mentioned polyoxonium skeleton is contained. The viscosity of the polymer compound is lowered. Therefore, the viscosity of the resin layer formed by using the chemically amplified negative-type photoresist material containing the polymer compound of the polyfluorene skeleton described above is also lowered.

The polymer compound having a polyfluorene skeleton having a repeating unit represented by the above formula (7) can be hydroquinone represented by the following structural formula (8) by the presence of a catalyst (1,4-double (two) Any one or both of methyl mercapto)benzene and a dihydroorganoorganoxane represented by the following formula (9), a phenol compound having two allyl groups represented by the following formula (10), and the following The so-called "hydrazine hydrogenation" polymerization reaction of any one or both of the compounds having two allyl groups represented by the formula (11) and the phenol compound having two allyl groups represented by the following formula (12) Obtain; [41] 【化42】 (wherein R ³ , R ⁴ , and m are the same as defined above.) (wherein Z, R ⁵ , R ⁶ , n, and x are the same as described above.) [Chem. 44] (wherein, V, R ⁷ , R ⁸ , p, and y are the same as described above.) (wherein T and R ^{9 are the} same as above.).

The phenol compound having two allyl groups represented by the above formula (12) is preferably a compound represented by the following formula (13) and a compound represented by the following formula (14). 【化46】 (wherein R ^{9 is the} same as above, and s is a positive number from 1 to 12.) (wherein R ^{9 is the} same as above.)

First, either or both of hydroquinone represented by the above structural formula (8) and dihydroorganoboxane represented by the above formula (9), and the above formula (10) are represented by 2 Allyl phenol compound, compound represented by the above formula (11) having two allyl groups and having an epoxy group, and a phenol compound having two allyl groups represented by the above formula (12) It is preferred that the compound represented by the above formula (13) having two allyl groups and having an alcoholic hydroxyl group or the phenol compound having two allyl groups represented by the above formula (14) is carried out in the presence of a catalyst. Description of the ideal conditions for the "hydrazine hydrogenation" polymerization.

Then, in order to obtain a phenol compound having two allyl groups represented by the above formula (12), in particular, a compound having two allyl groups and having an alcoholic hydroxyl group represented by the above formula (13), or the above-mentioned compound A suitable synthesis method of a phenol compound having two allyl groups represented by the formula (14) will be described.

Then, after preparing a polymer compound containing a polyfluorene skeleton having an alcoholic or phenolic hydroxyl group obtained by a hydrogenation polymerization of hydrazine, a part of an alcoholic or phenolic hydroxyl group of the polymer compound containing a polyfluorene skeleton is obtained. The reaction in which all or a dicarboxylic anhydride is reacted to introduce a carboxyl group will be described.

First, an explanation will be given of the ideal conditions for the "hydrazine hydrogenation" polymerization reaction carried out in the presence of a catalyst. Further, the weight average molecular weight of the polymer compound containing a polyfluorene skeleton of the present invention can be adjusted by adjusting the phenol compound having two allyl groups represented by the above formula (10), and the above formula (11) The allyl compound, the total number of allyl groups of the compound having two allyl groups represented by the above formula (12), the hydroquinone represented by the above structural formula (8), and the above formula (9) It is easily controlled by the ratio of the total number of hydroquinone groups of the dihydroorganoorganosiloxane (the total number of allyl groups / the total number of hydroquinone groups). Or by using the above specific epoxy group-containing compound having 2 allyl groups, a specific phenol compound having 2 allyl groups, and a specific isocyanuric acid skeleton having 2 allyl groups. The compound, and the hydroquinone and the dihydroorganosiloxane are used, for example, a monoallyl compound such as o-allylphenol or a hydroquinone or monohydroquinone such as triethylhydrofuran. The oxyalkylene is used as a molecular weight regulator to easily control the above weight average molecular weight.

In the above polymerization reaction, the catalyst may, for example, be a platinum group metal monomer such as platinum (including platinum black), ruthenium or palladium; H ₂ PtCl ₄ · xH ₂ O, H ₂ PtCl ₆ · xH ₂ O, NaHPtCl ₆ · xH ₂ O, KHPtCl ₆ · xH ₂ O, Na ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₄ · xH ₂ O, PtCl ₄ · xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · xH ₂ O (where x It is preferably an integer of 0 to 6, especially 0 or 6. Preferably, the platinum chloride, the chloroplatinic acid, and the chloroplatinate; the alcohol-modified platinum chloride acid (US Patent No. 3,220,972); A complex of chloroplatinic acid and an olefin (U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, U.S. Patent No. 3,775,452); platinum group, palladium and other platinum group metals supported on alumina, cerium oxide , carbon and other carriers; 铑-olefin complex; chloroform (triphenylphosphine) ruthenium (so-called WILKINSON catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl-containing ruthenium A complex of an oxane (especially a cyclic siloxane containing a vinyl group). The amount used is a catalyst amount, and it is usually preferably 0.001 to 0.1% by mass based on the total amount of the reaction polymer in terms of the platinum group metal.

In the above polymerization reaction, a solvent may be used as needed. A solvent such as a hydrocarbon solvent such as toluene or xylene is preferred. With respect to the above polymerization conditions, from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably, for example, 40 to 150 ° C, especially 60 to 120 ° C. The polymerization time depends on the type and amount of the polymer, but in order to prevent moisture intervening in the polymerization system, it is preferably about 0.5 to 100 hours, especially 0.5 to 30 hours. In this manner, after the completion of the polymerization reaction, when the solvent is used, the solvent is distilled off to prepare a polymer compound containing a polyfluorene skeleton having a repeating unit represented by the above formula (7).

Hereinafter, an ideal synthesis method will be described for the synthesis of a bis(4-hydroxy-2-allylphenyl) derivative having an alcoholic hydroxyl group represented by the above formula (12) or the above formula (13).

As a method for synthesizing one of the compounds represented by the above formula (12), a compound having a ketone and an alcoholic hydroxyl group represented by the following formula (15-1) can be used as a starting material. 【化48】 (wherein, R ⁹ and T are the same as above.)

First, an alcoholic hydroxyl group represented by the following formula (15-2) can be obtained by condensing a compound having a ketone and an alcoholic hydroxyl group represented by the above formula (15-1) under acidic conditions with 2 equivalents of phenol. Bisphenol derivatives. 【化49】 (wherein, R ⁹ and T are the same as above.)

Then, the bisphenol derivative having an alcoholic hydroxyl group represented by the above formula (15-2) and 2 equivalents of a halogenated propylene are reacted in an aprotic polar solvent under basic conditions using potassium carbonate to obtain the following A compound in which a hydrogen atom of a hydroxy group of a phenol represented by the formula (15-3) is substituted with an allyl group. 【化50】 (wherein, R ⁹ and T are the same as above.)

A compound in which a hydrogen atom of a hydroxy group represented by the above formula (15-3) is substituted with an allyl group is dissolved in a high boiling point solvent such as dimethylaniline, and is heated at a high temperature in the vicinity of 180 ° C to give a Kreisen weight. The Claisen Rearrangement reaction can obtain a bis(4-hydroxy-2-allylphenyl) derivative having an alcoholic hydroxyl group represented by the above formula (12) for the purpose of allyl transfer at the 2-position of phenol. .

On the other hand, as another preferred synthesis method of the compound represented by the above formula (12), a method of using a compound having a ketone or a carboxylic acid represented by the following formula (15-4) as a starting material can be mentioned. 【化51】 (wherein R ^{9 is the} same as defined above. T' represents a single bond or an alkylene group having 1 to 9 carbon atoms.)

The compound having a ketone and a carboxylic acid represented by the above formula (15-4) can be obtained by condensation of a bisphenol represented by the following formula (15-5) with a phenol condensed under the above acidic conditions and 2 equivalents of a phenol. Things. 【化52】 (wherein, R ⁹ and T' are the same as above.)

Further, the compound represented by the above formula (15-5) and 3 equivalents of a halogenated propylene are reacted under the same conditions as in the case of obtaining the above allyl ether, whereby a compound represented by the following formula (15-6) can be obtained. At this time, among the above-mentioned three equivalents of the halogenated propylene, two equivalents of the halogenated propylene are substituted with the hydrogen atom of the hydroxyl group of the phenol of the compound represented by the above formula (15-5) to the allyl group and the remaining one equivalent of the halogenated propylene is passed. The hydrogen atom of the carboxylic acid of the compound represented by the formula (15-5) is substituted with an allyl group, whereby a compound represented by the following formula (15-6) which is an allyl carboxylate can be obtained. 【化53】 (wherein, R ⁹ and T' are the same as above.)

Further, the compound represented by the above formula (15-6) is dissolved in an aprotic solvent such as tetrahydrofuran or toluene, and a solution of 1 equivalent or more, preferably 1 to 1.5 equivalents of Red-aluminum is placed at 0 ° C. The addition reaction of the carboxylic acid moiety can be easily carried out by adding and stirring at a temperature of from 0 ° C to 15 ° C at ~30 ° C, and the same general formula (15) as the compound represented by the above formula (15-3) can be obtained. -7) The compound indicated. 【化54】 (wherein, R ⁹ and T' are the same as above.)

Then, the compound represented by the above formula (15-7) can be obtained by the above-described Claissen rearrangement reaction, and the alcoholic property represented by the above formula (12) which has the purpose of allyl transfer at the 2-position of the phenol can be obtained. The bis(4-hydroxy-2-allylphenyl) derivative of the hydroxy group is a derivative represented by the following formula (15-8). 【化55】 (wherein, R ⁹ and T' are the same as above.)

In the series of methods for obtaining a bis(4-hydroxy-2-allylphenyl) derivative having an alcoholic hydroxyl group represented by the above formula (12), it is preferred to use bisphenolic acid (15- The compound represented by 9) is preferably a bisphenol derivative having a carboxylic acid represented by the above formula (15-5). That is, bisphenolic acid is industrially inexpensive and easy to obtain, and can be used as an example of a suitable starting material. 【化56】

When a bisphenolic acid of a suitable raw material is used, the bis(4-hydroxy-2-allylphenyl) derivative having an alcoholic hydroxyl group is a compound represented by the following formula (15-10), which is used for the above The hydrogenation of hydrazine is most desirable. 【化57】

On the other hand, the following formula (14) represents a phenol compound having two allyl groups, and a compound having a ketone represented by the following formula (15-1) is also used as a starting point in which T is a benzene ring compound. As the raw material, a compound having two allyl groups represented by the following formula (14) and having a phenolic hydroxyl group can be obtained. Examples of the compound represented by the following formula (15-1) which is a starting material include 4-hydroxybenzenedialdehyde and 4-hydroxyacetophenone which are ideal compounds. By condensing these starting materials under acidic conditions with 2 equivalents of 2-allylphenol, bis(4-hydroxy-2-allylbenzene represented by the following formula (14) having a phenolic hydroxyl group can be obtained. Base) derivative. 【化58】 (wherein, R ⁹ and T are the same as above.) (wherein R ^{9 is the} same as above.)

Next, a description will be given of a reaction in which a carboxyl group is introduced by reacting all or a part of a hydroxyl group of a polymer compound containing a polyoxymethylene skeleton having an alcoholic or phenolic hydroxyl group obtained by a hydrogenation polymerization reaction with a dicarboxylic acid anhydride.

In the bis(4-hydroxy-2-allylphenyl) derivative having a carboxylic acid represented by the following formula (15-11), the polyfluorene skeleton-containing polymer of the present invention can also be obtained by the above-described hydrazine hydrogenation method. a compound, but when a bis(4-hydroxy-2-allylphenyl) derivative having a carboxylic acid represented by the following formula (15-11) is used, the hydroquinone represented by the above structural formula (8) is sometimes used. The Si-H group of the benzene and the dihydroorganoorganosiloxane represented by the above formula (9) reacts with the above-mentioned carboxylic acid in the hydrogenation of hydrazine, and the polymer compound containing the polyfluorene skeleton of the present invention which is the object of interest cannot be obtained. Therefore, as described above, after preparing a polymer compound having an alcoholic or phenolic hydroxyl group containing a polyfluorene skeleton to form an intermediate, all or a part of the alcoholic or phenolic hydroxyl group of the intermediate is reacted with a dicarboxylic anhydride. Further, it is preferable to introduce a carboxyl group, and according to this method, a polymer compound containing a polyfluorene skeleton of the present invention can be obtained. 【化60】 (wherein, R ⁹ and T are the same as above.)

As a method of reacting all or a part of the hydroxyl group of the polymer compound containing a polyoxonium skeleton having an alcoholic or phenolic hydroxyl group obtained by the above-mentioned hydrazine hydrogenation polymerization reaction with a dicarboxylic anhydride, the obtained polycondensation is first obtained. The polymer compound of the oxime skeleton is dissolved in 4 times by weight of a solvent. For the W in the above formula (7), that is, the molar ratio of the alcoholic hydroxyl group or the phenolic hydroxyl group to the molar ratio k and l, the appropriate molar equivalent of the dicarboxylic anhydride is added, and the triethylamine is compared with the alcoholic hydroxyl group. Or the phenolic hydroxyl group is added in an equivalent amount, and the mixture is stirred at a temperature of from room temperature to 50 ° C for several hours and reacted to introduce a carboxyl group into a polymer compound containing a polyfluorene skeleton. The equivalent of the dicarboxylic acid anhydride to be reacted refers to the ratio of the repeating unit represented by the above formula (1) and the above formula (7), that is, (g + h) / (k + 1). For example, when the dicarboxylic acid anhydride of the reaction is 1 equivalent, a carboxyl group is introduced into all the alcoholic hydroxyl groups of the unit of the above formula (7), and e in the above formula (1) becomes e=0, and f becomes f=0. . The introduction ratio of the carboxyl group, that is, the ideal range of g and h in the above formula (1) is as described above.

The carboxylic acid introduced in this manner is represented by a unit of U in the above formula (1), and U is represented by the above formula (5). Further, R ¹⁰ in the above formula (5) can be represented by the following formula (6). 【化61】 (wherein, the dotted line represents a bond, and R ¹¹ to R ¹⁴ are each a different or the same substituent, and represent a hydrogen atom, a halogen atom, a linear, branched, cyclic alkyl group having a carbon number of 1 to 12, In the aromatic group, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may each be bonded to each other to form a substituted or unsubstituted cyclic structure having 1 to 12 carbon atoms. j is any one of 1 to 7.

In addition, the dicarboxylic acid anhydride which reacts all or a part of the hydroxyl group of the polymer compound containing a polyoxymethylene skeleton having an alcoholic or phenolic hydroxyl group can be represented by the following formula (16). 【化62】 (wherein, R ¹¹ to R ¹⁴ and j are the same as described above.)

Preferred examples of the dicarboxylic acid anhydride include succinic anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, sebacic anhydride, sebacic anhydride, and the following structures. The compound or the like is an ideal example. 【化63】

The polymer compound containing a polyfluorene skeleton having the structure represented by the above formula (5) obtained in this manner is suitable as a base resin of a chemically amplified negative-type photoresist material, and can improve metal wiring such as copper and aluminum, and an electrode. The problem of peeling on the substrate, especially on a substrate such as tantalum nitride. The reason why the peeling can be improved is considered to be that the structural portion represented by the above formula (5) introduced into the polymer compound having a polyfluorene skeleton improves the interaction with the substrate. The pattern formed by using a chemically amplified negative-type photoresist material containing a polymer compound containing a polyfluorene skeleton of the structural moiety represented by the above formula (5) is remarkably lacking in adhesion to a substrate.

On the other hand, as a result of introducing a structural portion represented by the above formula (5) into a polymer compound containing a polyfluorene skeleton, general-purpose tetramethylammonium hydroxide (for general use of a chemically amplified negative-type photoresist material) The solubility of the developing solution of the aqueous alkali solution of the TMAH) aqueous solution has an effect of improving. The chemically amplified negative-type photoresist material desirably has high solubility in a developing solution for an unexposed portion. That is, when the fine pattern is imaged, if the solubility of the unexposed portion with respect to the developer is low, there may be a case where a residue is dissolved at the bottom of the pattern or a tail occurs between the pattern and the substrate, but the use of the present invention is employed. In the pattern formed by the chemically amplified negative-type photoresist material of the polymer compound of the polyoxygen skeleton, as described above, the solubility of the unexposed portion in the aqueous alkali solution for the developer is improved, whereby the dissolution residue at the bottom of the pattern can be solved, This type of problem occurs with smearing.

The polymer compound containing a polyfluorene skeleton of the present invention has a repeating unit represented by the following formula (24) and has a weight average molecular weight of 3,000 to 500,000. 【化64】

In the above formula (24), R ²¹ to R ²⁴ may be different or the same, and may include a carbon number of 1 to 15 of an oxygen atom, preferably a monovalent organic group having 1 to 10 carbon atoms, and R ¹⁸ and R ¹⁹ may be different or the same, and may represent a carbon number of 1 to 28, preferably a carbon number of 1 to 15, more preferably a monovalent organic group having 1 to 10 carbon atoms. Specific examples thereof include a linear, branched or cyclic alkyl group, a vinyl group, an allyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group or a cyclohexyl group. a linear, branched or cyclic alkenyl group such as a propenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group; an aryl group such as a phenyl group or a tolyl group; a benzyl group, a phenylethyl group or a methoxy group; An aralkyl group such as phenylethyl group. m' is an integer from 0 to 100, and o is an integer from 0 to 100. Further, c', d', e', and f' are 0 or a positive number, and a', b', g', and h' are positive numbers. Only a'+b'+c'+d'+e'+f'+g'+h'=1. Further, X' is a divalent organic group represented by the following formula (25) or (26), Y is a divalent organic group represented by the following formula (3), and W is represented by the following formula (4) The divalent organic group, U is a divalent organic group represented by the following formula (5). 【化65】 (The broken line represents a bond, and each of R ⁵ and R ⁶ is an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different from each other. x is any one of 0, 1, and 2.) 66] (wherein, V is a divalent organic group selected from any one of the following: [67] The dotted line represents the bond and p is 0 or 1. R ⁷ and R ^{8 are} each an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and may be the same or different. y is any of 0, 1, and 2. ) 【化68】 (wherein, the dotted line represents a bond, T represents an alkyl group having a carbon number of 1 to 10 or a divalent aromatic group, and R ⁹ represents a hydrogen atom or a methyl group.) (wherein, the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group.)

Further, in the above formula (24), о is an integer of 1 to 100, preferably 1 to 80, and R ²¹ to R ²⁴ may be the same or different, and are a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ¹⁸ is the following The phenyl substituent having a hydroxyl group or an alkoxy group represented by the formula (27), R ¹⁹ and R ²¹ to R ²⁴ may be the same or different and may also contain a monovalent organic group having 1 to 10 carbon atoms of an oxygen atom. The group is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a phenyl substituent having a hydroxyl group or an alkoxy group represented by the following formula (27) which is the same as or different from R ¹⁸ . 【化70】 (wherein, r is an integer of 0 to 10, and R ²⁰ is a hydroxyl group or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms.)

Further, in the phenyl substituent represented by the above formula (27), the hydroxy group or the alkoxy group may be substituted in any of the ortho, meta and para positions. When R ²⁰ is an alkoxy group, the carbon number is from 1 to 12, preferably from 1 to 4.

Specific examples of the phenyl substituent represented by the above formula (27) include the groups represented by the following formula (28). Further, in the following formula (28), the straight line accompanying the wavy line represents the bonding hand. 【化71】 【化72】

For example, the polymer compound containing a polyfluorene skeleton has a biphenol skeleton represented by the above formula (25) or (26). Thus, the polymer compound containing a polyfluorene skeleton of the present invention is suitable as a base resin of a chemically amplified negative-type photoresist material, and can improve a metal wiring such as copper or aluminum, an electrode, a substrate, and particularly a substrate such as tantalum nitride. The problem of the divestiture.

In addition, when a structural part represented by the above formula (25) or (26) is introduced into a polymer compound containing a polyfluorene skeleton, a high Tg and an excellent mechanical strength are imparted to the hardened film because of a rigid structure having a small degree of freedom. Reliable, and due to its compact structure, it is possible to obtain an effect of improving the solubility of a developing solution of an aqueous alkali solution of a general-purpose tetramethylammonium hydroxide (TMAH) aqueous solution used for a chemically amplified negative-type photoresist material.

On the other hand, in the case of using a polymer compound having a polyfluorene skeleton-containing polymer compound of the present invention having a phenyl substituent represented by the above formula (27) as a base resin, a chemically amplified negative-type photoresist material can be used for pattern formation. Improve the crosslinking reactivity of the exposed portion. The reason is considered to be that a cross-linking point is also present on the decane, whereby the cross-linking point in the polymer compound containing the polyfluorene skeleton is remarkably increased, and the reaction with the cross-linking agent described later proceeds more. As described above, by improving the crosslinking reactivity of the exposed portion, the solubility of the exposed portion with respect to the developer is reduced.

As described above, by using the polymer compound containing a polyfluorene skeleton of the present invention as a base resin of a chemically amplified negative-type photoresist material, the solubility of the unexposed portion to the developer can be improved, and the exposed portion can be used for the developer. The solubility is extremely reduced. Therefore, the difference in the dissolution rate between the exposed portion and the unexposed portion is increased, and the dissolution contrast can be increased, and formation of a finer pattern can be expected. That is, the polymer compound containing a polyfluorene skeleton of the present invention is suitable as a base resin of a chemically amplified negative type resist material.

Furthermore, the present invention provides a chemically amplified negative-type photoresist material comprising: (A) the above-mentioned polymer compound containing a polyfluorene skeleton, and (B) photoacid generation which is decomposed by light having a wavelength of 190 to 500 nm to generate an acid. And (C) a crosslinking agent, which is selected from one or more of the following compounds: an amine condensate obtained by modifying formaldehyde or a formaldehyde-alcohol, and an average of two or more methylol groups or alkane in one molecule The phenolic compound of the oxymethylol group and the hydrogen atom of the hydroxyl group of the polyhydric phenol are substituted with the epoxy propyl group, and the hydrogen atom of the hydroxyl group of the polyhydric phenol is substituted with the substituent represented by the following formula (C-1). a compound obtained, and a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2) [Chem. 73] (wherein, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and z represents 1 or 2.) (D) Solvent, and (E) Alkaline Compound.

(B) The photoacid generator can be used to generate an acid by irradiation with light having a wavelength of 190 to 500 nm, and it becomes a hardening catalyst. The polymer compound containing a polyfluorene skeleton of the present invention is excellent in compatibility with a photoacid generator, and various types of photoacid generators can be used. Such photoacid generators, for example, phosphonium salts, diazomethane derivatives, ethylene dioxane derivatives, β-keto oxime derivatives, diterpene derivatives, nitrobenzyl sulfonate derivatives, sulfonates Derivative, quinone imido-sulfonate derivative, oxime sulfonate derivative, imino sulfonate derivative, three Derivatives, etc.

The above sulfonium salt is, for example, a compound represented by the following formula (17). (R ¹⁵ ) _j' M ⁺ K ^- (17) (wherein R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, and a carbon number of 6 to 12 An aryl group or an aralkyl group having 7 to 12 carbon atoms, M ⁺ represents ruthenium or osmium, K ^- represents a non-nucleophilic relative ion, and j' represents 2 or 3.

In the above R ¹⁵ , the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-oxocyclohexyl group, a norbornyl group, an adamantyl group or the like. An aryl group, for example, a phenyl group; an alkoxyphenyl group such as an ortho, meta or para-methoxyphenyl group, an ethoxyphenyl group, a meta or para-tert-butoxyphenyl group; An alkylphenyl group such as 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl or dimethylphenyl. The aralkyl group is, for example, a group such as a benzyl group or a phenethyl group.

Examples of the non-nucleophilic counter ion of the above K ^- include halide ions such as chloride ions and bromide ions; trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate. Isofluoroalkylsulfonate; sulfonate such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate; methanesulfonate, butanesulfonate Is an alkyl sulfonate or the like.

The above diazomethane derivative may, for example, be a compound represented by the following formula (18). 【化74】 (wherein R ¹⁶ may be different or the same, and represents a linear, branched or cyclic alkyl or halogenated alkyl group having from 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogenated aryl group, Or an aralkyl group having a carbon number of 7 to 12.)

In the above R ¹⁶ , the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group or an adamantyl group. Halogenated alkyl group, for example, trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, and the like. Aryl, for example: phenyl; o-, m- or p-methoxyphenyl, ethoxyphenyl, m- or p-t-butoxyphenyl alkoxyphenyl; 2-, 3- or 4- An alkylphenyl group such as a methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group or a dimethylphenyl group. A halogenated aryl group such as fluorophenyl group, chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group or the like. An aralkyl group, for example, a benzyl group, a phenethyl group or the like.

Specific examples of such a photoacid generator include diphenylphosphonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-butoxyphenyl)phenylsulfonium, and diphenylphosphonium p-toluenesulfonate. , p-toluenesulfonic acid (p-butoxyphenyl)phenylhydrazine, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-butoxyphenyl)diphenylphosphonium, three Bis(p-butoxyphenyl)phenyl fluoromethanesulfonate, ruthenium trifluoromethanesulfonate (p-butoxyphenyl) fluorene, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl)diphenylphosphonium, p-toluenesulfonic acid bis(p-butoxyphenyl)phenylhydrazine, p-toluenesulfonic acid ginseng (p-butoxyphenyl)phosphonium , triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium triflate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate ( 2-sided oxycyclohexyl) fluorene, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) fluorene, dimethylphenyl sulfonium trifluoromethanesulfonate, dimethylphenyl p-toluenesulfonate Bismuth, dicyclohexylphenyl sulfonium trifluoromethanesulfonate, dicyclohexylphenyl sulfonium p-toluenesulfonate, hexafluoroantimonic acid Anthracene salt such as phenyl(4-thiophenoxyphenyl)anthracene; bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylsulfonyl) Nitrogen methane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl) Diazomethane, bis(t-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(t-butyl Sulfhydryl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(second amylsulfonyl)diazomethane, bis( Third amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(third pentyl) Diazomethane derivatives such as sulfonyl)diazomethane, 1-tripentylsulfonyl-1-(tert-butylsulfonyl)diazomethane; bis-o-(p-toluenesulfonyl) -α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylethylene肟, double-o-(pair Phenylsulfonyl)-2,3-pentanedione ethanedioxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione ethanedioxime, bis-o-(n-butyl) Alkylsulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)- α-Dicyclohexylethylenediazine, bis-o-(n-butanesulfonyl)-2,3-pentanedione ethanedioxime, bis-o-(n-butanesulfonyl)-2-methyl -3,4-pentanedione ethanedioxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethyl Ethylene dioxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(t-butanesulfonyl)-α-di Methylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime , bis-o-(phenylsulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorophenylsulfonyl)-α-dimethylglyoxime, bis-o-(pair Tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylsulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl) -Anthracene derivative such as -α-dimethylglyoxime; α-(benzoquinoneimido)-4-methylbenzene An oxime sulfonate derivative such as acetonitrile; a β-keto oxime derivative such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane or 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane a diterpene derivative such as diphenyldifluorene or dicyclohexyldifluoride; 2,6-dinitrobenzyl p-toluenesulfonate; 2,4-dinitrobenzyl p-toluenesulfonate; Base sulfonate derivatives; 1,2,3-shen (methanesulfonyloxy)benzene, 1,2,3-paran (trifluoromethanesulfonyloxy)benzene, 1,2,3-parameter (pair) a sulfonate derivative such as toluenesulfonyloxy)benzene; phthalic acid imine trifluoromethanesulfonate, phthalic acid imine tosylate, 5-northene 2,3 -Dicarboxy quinone imine trifluoromethanesulfonate, 5-northene 2,3-dicarboxy quinone imine tosylate, 5-northene 2,3-dicarboxy quinone imine a quinone imine sulfonate derivative such as butyl sulfonate or n-trifluoromethylsulfonyloxynaphthyl imine; (5-(4-methylphenyl)sulfonyloxyimino-5H -thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H- Iminosulfonic acid such as thiophene-2-ylidene)-(2-methylphenyl)-acetonitrile 2-methyl-2 [(4-methylphenyl) sulfonyl acyl] -1 - [(4-methylthio) phenyl] -1-propane. Among these, sulfhydrido sulfonates, imidosulfonates, oxime sulfonates, and the like are preferred. Further, one or two or more kinds of the photoacid generators may be used.

Further, the blending amount of the photoacid generator described above is based on the viewpoint of the light absorption of the photoacid generator itself and the photocurability of the thick film, and is 0.05 with respect to (A) the polymer compound containing the polyfluorene skeleton. It is preferable that it is preferably 20 parts by mass, especially 0.2 to 5 parts by mass.

(C) The crosslinking agent may be one or more selected from the group consisting of an amine condensate modified with formaldehyde or formaldehyde-alcohol, and an average of two or more methylol groups or alkoxy groups in one molecule. The hydroxy group of the hydroxymethyl group and the hydrogen atom of the hydroxyl group of the polyhydric phenol are substituted with the epoxy propyl group, and the hydrogen atom of the hydroxyl group of the polyhydric phenol is substituted with the substituent represented by the following formula (C-1). And a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2). 【化75】 (wherein, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having a carbon number of 1 to 6, and z represents 1 or 2.)

The above-mentioned amine-based condensate modified with formaldehyde or formaldehyde-alcohol, for example, a melamine condensate modified with formaldehyde or formaldehyde-alcohol, or a urea condensate modified with formaldehyde or formaldehyde-alcohol.

Further, the preparation of the melamine condensate obtained by modifying formaldehyde or formaldehyde-alcohol may be, for example, modified by methylolation of melamine monomer by a known method, or further alkoxylation with an alcohol. It is modified to be a modified melamine represented by the following formula (19). Further, the above alcohol is preferably a lower alcohol, and for example, an alcohol having 1 to 4 carbon atoms is preferred.

【化76】 (wherein R ¹⁷ may be different or the same, and is a methylol group, an alkoxymethyl group having an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, but at least one is a methylol group or an alkane. Oxymethyl group. The above R ^{17 is} , for example, an alkoxymethyl group such as a methylol group, a methoxymethyl group or an ethoxymethyl group, or a hydrogen atom.

Specific examples of the modified melamine represented by the above formula (19) include trimethoxymethyl-hydroxymethyl melamine, dimethoxymethyl-hydroxymethyl melamine, trimethylol melamine, and hexamethylol. Melamine, hexamethoxymethylol melamine, and the like. Next, the modified melamine represented by the formula (19) or a multipolymer thereof (for example, an oligomer such as a dimer or a trimer) is subjected to addition condensation polymerization by a conventional method and formaldehyde to obtain a desired molecular weight, and can be utilized. A melamine condensate modified with formaldehyde or formaldehyde-alcohol.

Further, the above-mentioned urea condensate obtained by modifying formaldehyde or formaldehyde-alcohol can be modified, for example, by methylolation of formaldehyde of a desired molecular weight by a known method, or further by using an alcohol Modified by oxylation. Specific examples of the above-mentioned urea condensate modified by formaldehyde or formaldehyde-alcohol, for example, methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate Wait. In addition, one type or two or more types of the modified melamine condensate and the modified urea condensate may be used in combination.

Secondly, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, such as (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2', 6,6'-tetramethoxymethylbisphenol A, a compound represented by the following formula (C-3) to (C-7), and the like. 【化77】

On the other hand, a compound obtained by substituting a hydrogen atom of a hydroxyl group of a polyhydric phenol with a glycidyl group, for example, bisphenol A, stilbene (4-hydroxyphenyl)methane, 1,1,1-cis (4-hydroxybenzene) a compound obtained by reacting a hydroxyl group of ethane with epichlorohydrin in the presence of a base. A preferred example of the compound in which the hydrogen atom of the hydroxyl group of the polyhydric phenol is substituted with a propylene group is specifically a compound represented by the following formulas (C-8) to (C-14). 【化78】 (wherein t is 2≦t≦3.) One or two kinds of compounds obtained by substituting a hydrogen atom of a hydroxyl group of these polyhydric phenols with a propylene group can be used as a crosslinking agent.

In addition, the compound represented by the following formula (C-15) is a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1) and has two or more substituents. 【化79】 (In the formula, the dotted line represents the bond.) (where u is 1≦u≦3.)

On the other hand, a compound containing two or more nitrogen atoms having a glycidyl group represented by the following formula (C-2) can be represented by the following formula (C-16). 【化81】 (wherein, the dotted line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and z represents 1 or 2.) (wherein Q represents a linear, branched, cyclic alkyl group or a divalent aromatic group having 2 to 12 carbon atoms.) A compound represented by the above formula (C-16), for example, (C-17)~(C-20) represents a compound. 【化83】

On the other hand, a compound represented by the following formula (C-21) can also be preferably used as the compound containing two or more nitrogen atoms having a glycidyl group represented by the above formula (C-2). 【化84】 One or two kinds of compounds containing two or more nitrogen atoms having a glycidyl group represented by the above formula (C-2) can be used as a crosslinking agent.

Further, the above-mentioned crosslinking agent is a component which can be easily formed into a pattern by (A) a polymer compound containing a polyfluorene skeleton, and is a component which further enhances the strength of the cured product. The weight average molecular weight of such a crosslinking agent, and the viewpoint of photocurability and heat resistance are preferably from 150 to 10,000, particularly preferably from 200 to 3,000.

Further, the above-mentioned crosslinking agents may be used alone or in combination of two or more. In addition, the amount of the above-mentioned crosslinking agent is considered to be the quality of the polymer compound containing the polyoxyxene skeleton as a viewpoint of the reliability of the film for electrical and electronic component protection by photocurability and post-hardening. The amount is preferably 0.5 to 50 parts by mass, particularly preferably 1 to 30 parts by mass.

(D) The solvent can be used by dissolving (A) a polymer compound containing a polyfluorene skeleton, (B) a photoacid generator, and (C) a crosslinking agent. Such solvents, for example, ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1- Alcohols such as methoxy-2-propanol and 1-ethoxy-2-propanol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, Ethers such as diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3 - Ethyl ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, γ-butyrolactone, and the like, and the like. In particular, it is preferred to use ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone or a mixed solvent of the most excellent solubility of the photoacid generator.

The blending amount of the above solvent, considering the compatibility, viscosity, and coating property of the chemically amplified negative-type photoresist material, relative to (A) a polymer compound containing a polyfluorene skeleton, and (B) a photoacid generator The total amount of the blending amount of the (C) crosslinking agent is preferably from 50 to 2,000 parts by mass, particularly preferably from 100 to 10,000 parts by mass, based on 100 parts by mass.

Further, in the chemically amplified negative-type photoresist material of the present invention, a basic compound may be added as the component (E) as needed. As the basic compound, a compound which can suppress the diffusion rate of the acid generated by the photoacid generator in the diffusion of the photoresist film is suitable. By blending such a basic compound, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate and the environment are reduced, and the exposure margin, the pattern shape, and the like can be improved.

Examples of such a basic compound include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, carboxyl group-containing compounds, and sulfonyl group-containing nitrogen compounds. The nitrogen-containing compound of the hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, the alcohol-containing nitrogen-containing compound, the guanamine derivative, and the quinone imine derivative may, for example, be a compound represented by the following formula (20). N(α) _q (β) _3-q (20)

Where q is 1, 2 or 3. The side chain α may be different or the same, and is any of the substituents represented by the following general formulae (21) to (23). The side chain β may be different or the same, and may represent a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain an ether bond or a hydroxyl group. Further, the side chains α may be bonded to each other to form a ring. 【化85】 Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are a hydrogen atom or a linear or branched carbon number of 1 to 20. Or a cyclic alkyl group, which may also contain one or more hydroxyl groups, ether bonds, ester bonds, and lactone rings. R ³⁰³ is a single bond or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may also contain 1 Or a plurality of hydroxyl groups, ether bonds, ester bonds, lactone rings. Also, * represents the end of the bond.

The above primary aliphatic amines, such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, second butylamine, third butylamine, pentylamine, third pentylamine, cyclopentane Amine, hexylamine, cyclohexylamine, heptylamine, octylamine, decylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, and the like.

The above secondary aliphatic amines, such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-second-butylamine, diamylamine, dicyclopentylamine, Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, diamine, diamine, di(dodecyl)amine, di(hexadecyl)amine, N,N-dimethylmethylene Amine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, and the like.

The above tertiary aliphatic amines, such as trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-second butylamine, triamylamine, tricyclopentylamine, three Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, tridecylamine, tridecylamine, tris(d)amine, tris(hexadecyl)amine, N,N,N',N'-tetra Isomethyldiamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

The above-mentioned mixed amines are, for example, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

The above aromatic amines and heterocyclic amines, such as aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methyl Aniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-di Nitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, three Aniline, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N -methylpyrrole, etc.), An azole derivative (for example Azole Oxazole, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan ( Furazane) derivative, dihydropyrrole derivative (eg dihydropyrrole, 2-methyl-1-dihydropyrrole, etc.), pyrrolidine derivative (eg pyrrolidine, N-methylpyrrolidine, pyrrolidone, N) -methylpyrrolidone, etc.), imidazoline derivatives, imidazolium derivatives, pyridine derivatives (eg pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)) Pyridine, lutidine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, A Oxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl Pyridine, aminopyridine, dimethylaminopyridine, etc.) Derivative, pyrimidine derivative, pyridyl Derivatives, pyrazoline derivatives, pyrazole derivatives, piperidine derivatives, piperidine derivative, a porphyrin derivative, an anthracene derivative, an isoindole derivative, a 1H-carbazole derivative, a porphyrin derivative, a quinoline derivative (for example, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative , porphyrin-derived derivative, quinazoline derivative, quinoxaline derivative, hydrazine Derivatives, anthracene derivatives, pteridine derivatives, carbazole derivatives, phenidine derivatives, acridine derivatives, brown Derivatives, 1,10-morpholine derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, and the like.

The above nitrogen-containing compound having a carboxyl group, such as an aminobenzoic acid, an anthracene carboxylic acid, or an amino acid derivative (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine) , histidine, isoleucine, glycine leucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyridin 2-carboxylic acid, methoxyalanine, etc.) and the like.

The above nitrogen-containing compound having a sulfonyl group, for example, 3-pyridinesulfonic acid, p-toluenesulfonic acid pyridine or the like.

The above nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, and an alcohol-containing nitrogen-containing compound, for example, 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydration , monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl) Porphyrin, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)per , 1-[2-(2-hydroxyethoxy)ethyl]piperidin , piperidine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-piperidinyl-1,2-propanediol, 3-pyrrolidinyl -1,2-propanediol, 8-hydroxyl 8-hydroxy-julolidine, 3-quinuclidinol, 3-terpineol, 1-methyl-2-pyrrolidineethanol, 1-aziridine ethanol, N-(2 - hydroxyethyl) phthalimide, N-(2-hydroxyethyl)isonicotinamine, and the like.

The above guanamine derivatives, such as formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethyl B Guanamine, acrylamide, benzamide, and the like. Further, the above quinone imine derivatives are, for example, phthalimide, amber imine, and maleimide.

The compound represented by the above formula (20) may be exemplified by gin [2-(methoxymethoxy)ethyl]amine, gin[2-(2-methoxyethoxy)ethyl]amine, and ginseng [ 2-(2-methoxyethoxymethoxy)ethyl]amine, gin[2-(1-methoxyethoxy)ethyl]amine, gin[2-(1-ethoxy B) Oxy)ethyl]amine, gin[2-(1-ethoxypropoxy)ethyl]amine, gin[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine ,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexadecane, 4,7,13,18-tetraoxa-1,10 -diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4,1 -aza-15-crown-5, 1-aza-18-crown-6, ginseng (2-formyloxyethyl)amine, ginseng (2-acetoxyethyl)amine, ginseng (2 -propenyloxyethyl)amine, ginseng (2-butoxyethyl)amine, ginseng (2-isobutyloxyethyl)amine, ginseng (2-pentyloxyethyl)amine, Ginseng (2-trimethylacetoxyethyl)amine, N,N-bis(2-acetoxyethyl)2-(ethyloxyethoxycarbonyl)ethylamine, ginseng (2-A) Oxycarbonyloxyethyl)amine, ginseng (2-t-butoxycarbonyloxyethyl)amine, ginseng [2-(2-o-oxypropoxy)ethyl] , [2-(methoxycarbonylmethyl)oxyethyl]amine, gin[2-(t-butoxycarbonylmethoxy)ethyl]amine, gin[2-(cyclohexyloxycarbonyl) Oxy)ethyl]amine, ginseng (2-methoxycarbonylethyl)amine, ginate (2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)2-(A Ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(ethoxy Ethylcarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(2-methyl Oxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyl Ethyl) 2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(2-acetoxyethoxycarbonyl)ethylamine, N , N-bis(2-hydroxyethyl)2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(methoxy) Carbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)2-(2-o-oxypropoxycarbonyl)ethylamine, N,N-bis(2-ethenyloxy) Ethyl) 2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2-(tetrahydrofuran) Methyloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)2-(tetrahydrofuranmethyloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)2 -[(2-Sideoxytetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)2-[(2-o-oxytetrahydrofuran-3-yl) Oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-methylmethoxyethyl)2-( 4-Methoxyoxybutoxycarbonyl)ethylamine, N,N-bis(2-methylmethoxyethyl) 2-(2-methyloxyethoxycarbonyl)ethylamine, N,N- Bis(2-methoxyethyl)2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2- Ethyloxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2 - ethoxylated ethyl) bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-Ethyloxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl) bis[2-(methoxycarbonyl) Ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxy) Ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-three Methylacetoxyethylamine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(t-butoxycarbonyloxy)B Amine, ginseng (methoxycarbonylmethyl)amine, ginseng (ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonyl) Methyl)amine, β-(diethylamino)-δ-valerolactone, but is not limited thereto.

Further, the basic compound may be used alone or in combination of two or more. In addition, it is preferable that the amount of the above-mentioned basic compound is 0 to 3 parts by mass, and particularly preferably 0.01 to 1 part by mass, based on 100 parts by mass of the polymer compound containing a polyfluorene skeleton. .

Further, in the chemically amplified negative-type photoresist material of the present invention, in addition to the above components (A) to (E), the additive component may be further blended. The light-absorbing agent which is conventionally used for the purpose of improving the light absorption efficiency, such as a surfactant or a photoacid generator which are conventionally used for the purpose of improving the coating property, may be mentioned.

The above surfactant is preferably an ionic one, for example, a fluorine-based surfactant, and specific examples thereof include perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkane amine oxides, and fluorine-containing organic germanium oxides. An alkyl compound or the like.

Commercially available products such as Fluorad "FC-4430" (manufactured by Sumitomo 3M Co., Ltd.), surflon "S-141" and "S-145" (above, Asahi Glass Co., Ltd.), Unidyne "DS-401", "DS-4031" and "DS-451" (above, Daikin Industries Co., Ltd.), Megafac "F-8151" (DIC system), "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd.) and so on. Among these, it is preferably Fluorad "FC-4430" (Sumitomo 3M (share) system) and "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd.).

The above light absorbing agent is, for example, a diaryl sulfonium, a diaryl fluorene, a 9,10-dimethyl hydrazine, a 9-fluorenone or the like.

The preparation of the chemically amplified negative photoresist material of the present invention is carried out in the usual manner. The chemically amplified negative-type photoresist material can be prepared by stirring and mixing the above components, followed by filtration with a filter or the like. When a photocurable dry film described later is produced, it can also be prepared in the same manner using this chemically amplified negative resist material.

In order to form a pattern using the chemically amplified negative-type photoresist material of the present invention prepared in the above manner, it can be carried out by a known lithography technique. For example, a chemically amplified negative-type photoresist material is applied by spin coating to a germanium wafer, a SiO ₂ substrate, a tantalum nitride substrate, or a substrate having a pattern such as a copper wiring, at 80 to 130 ° C, 50 to 600 A pre-baking condition of about seconds is performed to form a photoresist film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

In the spin coating method, the photoresist can be coated on the substrate by distributing the photoresist material to about 5 mL on the ruthenium substrate and then rotating the substrate. At this time, the film thickness of the photoresist film on the substrate can be easily adjusted by adjusting the rotation speed.

Then, a mask cover for forming a target pattern is placed on the photoresist film to irradiate high-energy rays having a wavelength of 190 to 500 nm such as i-rays and g-rays so that the exposure amount becomes about 1 to 5,000 mJ/cm ² , preferably It is about 100~2,000mJ/cm ² . By exposure in this manner, the exposed portions are crosslinked to form a pattern insoluble in the developer described later.

Then, if necessary, perform post-exposure baking (PEB) on a hot plate at 60 to 150 ° C for 1 to 10 minutes, preferably 80 to 120 ° C for 1 to 5 minutes.

It is then developed with a developing solution. The developer may be a solvent used in the preparation of the chemically amplified negative-type photoresist material of the present invention using a 2.38% TMAH aqueous solution. For example, an alcohol such as isopropyl alcohol (IPA) or a ketone such as cyclohexanone, or a glycol such as propylene glycol monomethyl ether is preferable. The development can be carried out by a usual method, for example, by immersing the patterned substrate in a developing solution or the like. Thereafter, washing, rinsing, drying, and the like may be performed as needed to obtain a photoresist film having a desired pattern. Further, when it is not necessary to form a pattern, for example, when a uniform film is formed, the content described in the above-described pattern forming method may be carried out in the same manner except that the mask is not used.

Further, it is preferable to use the oven and the hot plate to post-harden the photoresist film at a temperature of 100 to 250 ° C, preferably 150 to 220 ° C, and more preferably 170 to 190 ° C. If the post-hardening temperature is 100 to 250 ° C, it is preferable to increase the crosslinking density of the photoresist film, remove the remaining volatile components, and consider the adhesion, heat resistance, strength, and electrical properties of the substrate. Also, the post-hardening time can be set to 10 minutes to 10 hours.

The hardened film obtained in this manner is excellent in adhesion to a substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to a flux liquid, and such a hardened film is used as a semiconductor element for a protective film. The reliability is also excellent, especially to prevent cracking during temperature cycle test. In other words, the chemically amplified negative-type photoresist material of the present invention can be used as a protective film for electric and electronic parts, semiconductor elements, and the like.

Further, the present invention provides a photocurable dry film produced by using the above chemically amplified negative-type photoresist material.

First, the structure of the photocurable dry film of the present invention will be described. The photocurable dry film has a structure in which a photocurable resin layer is sandwiched between a support film and a protective film. Further, as the photocurable resin layer, a chemically amplified negative-type photoresist material of the present invention which is effective for forming a film for electrical and electronic component protection can be used. Such a photocurable dry film can form a fine pattern in a wide range of film thickness and wavelength range, and can be cured by a low temperature and then cured to have flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance. .

In the present invention, the photocurable resin layer of the photocurable dry film obtained by using the above chemically amplified negative photoresist material is solid, and the photocurable resin layer does not contain a solvent, so that no bubbles remain in the photohardening due to volatilization thereof. The inside of the resin layer and the flaw between the uneven substrate. In addition, the semiconductor element is becoming smaller, thinner, and multilayered, and the interlayer insulating layer tends to be thinner. However, considering the flatness and the high-low-difference coating on the uneven substrate, an appropriate film thickness range exists. Therefore, the film thickness of the photocurable resin layer is preferably from 10 to 100 μm, more preferably from 10 to 70 μm, even more preferably from 10 to 50 μm, from the viewpoint of flatness and high and low coverage.

Further, the viscosity of the photocurable resin layer is closely related to the fluidity, and the photocurable resin layer can exhibit appropriate fluidity in an appropriate viscosity ratio range and can penetrate into a narrow gap. Therefore, as described above, the photocurable dry film of the photocurable resin layer is formed by the chemically amplified photoresist material containing the polymer compound containing the polyfluorene skeleton of the present invention at an appropriate viscosity ratio, and is bonded to the tape. In the case of the uneven substrate, the photocurable resin layer is covered with the unevenness, and high flatness can be achieved. In addition, the polymer compound containing a polyfluorene skeleton which is a main component of the photocurable resin layer contains a siloxane chain, and has a low surface tension and can achieve higher flatness. Moreover, when the photocurable resin layer is adhered to the substrate in a vacuum environment, it is possible to more effectively prevent such a gap from occurring.

Next, the method for producing the photocurable dry film of the present invention will be described.

In the photocurable dry film of the present invention, the chemically amplified negative-type photoresist material used in forming the photocurable resin layer can be prepared by stirring and mixing the above components, followed by filtration with a filter or the like, which is chemically amplified. The negative photoresist material can be used as a material for forming a photocurable resin layer.

The support film used for the photocurable dry film of the present invention may be a single film or a multilayer film obtained by laminating a plurality of polymer films. The material may, for example, be a synthetic resin film such as polyethylene, polypropylene, polycarbonate or polyethylene terephthalate, and is preferably polyethylene terephthalate having appropriate flexibility, mechanical strength and heat resistance. The ester is preferred. Further, various processors such as corona treatment and coating release agent may be applied to the films. Commercially available products such as Cerapeel WZ (RX), Cerapeel BX8 (R) (above, Toray Film Processing Co., Ltd.), E7302, E7304 (above, Toyobo Co., Ltd.), Purex G31, Purex G71T1 (above, manufactured by Teijin DuPont Film Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (above, manufactured by Nippa Co., Ltd.).

The protective film used for the photocurable dry film of the present invention can be preferably the same as the above-mentioned support film, and it is preferred to use polyethylene terephthalate and polyethylene having appropriate flexibility. For the polyethylene terephthalate, the polyethylene terephthalate may be exemplified, and examples of the polyethylene include GF-8 (manufactured by Tamapoli Co., Ltd.) and PE film type 0 (Nippa). (share) system).

The thickness of the support film and the protective film is preferably from 10 to 100 μm, particularly preferably from 25 to 50 μm, in view of the stability of the production of the photocurable dry film and the prevention of the winding tendency of the winding core, that is, the so-called curl.

As the apparatus for producing a photocurable dry film, a film coater generally used for producing an adhesive article can be used. Film coater, for example: comma coater, reverse angle wheel coater, multiple coater, die coater, lip coater, lip reverse coater, direct gravure printing A coater, a reverse gravure coater, a three-bottom reverse coater, a 4-roll bottom feed reverse coater, and the like.

It can be manufactured by coating a chemically amplified negative photoresist material with a predetermined thickness when the support film is taken up from the roll-up shaft of the film coater and passed through the coating head of the film coater. After the film is formed on the support film and the photocurable resin layer is formed, it is passed through a hot air circulation oven at a predetermined temperature for a predetermined period of time, and is continuously dried on the support film to form a photocurable resin layer, and the photocurable resin layer and the photocurable resin layer are The protective film rolled out from the other winding shaft of the film coater passes through the laminating roll at a predetermined pressure, and is bonded to the photocurable resin layer on the support film, and then wound up in a film coater. The shaft is manufactured. In this case, the temperature of the hot air circulation oven is preferably 25 to 150 ° C, and the passage time is preferably 1 to 100 minutes, and the pressure of the laminating roller is preferably 0.01 to 5 MPa.

Next, a description will be given of a pattern forming method using the photocurable dry film produced in the above manner. In the pattern forming method of the photocurable dry film of the present invention, first, the protective film is peeled off from the photocurable dry film, and the photocurable resin layer is adhered to the substrate. Then, exposure is performed, and post-exposure heat treatment (post-exposure baking (hereinafter referred to as PEB)) is performed. Development is then carried out and, if necessary, post-hardening to form a patterned hardened film.

First, the photocurable dry film is adhered to the substrate using a film coating device. The substrate includes, for example, a tantalum wafer, a TSV wafer, a plastic, a ceramic, and various metal circuit boards. In particular, a substrate having a groove having a width of 10 to 100 μm and a depth of 10 to 120 μm is used. The filming device is preferably a vacuum laminator.

Specifically, the photocurable dry film is attached to the film coating apparatus, and the protective film of the photocurable dry film is peeled off, and the exposed photocurable resin layer is applied to a predetermined pressure in a vacuum chamber having a predetermined degree of vacuum. The substrate is adhered to the substrate at a predetermined temperature. Moreover, the table top temperature is preferably 60 to 120 ° C, and the pressure of the applicator roller is preferably 0 to 5.0 MPa, and the vacuum degree of the vacuum chamber is preferably 50 to 500 Pa.

Patterns can be formed using known lithography techniques after the adhesion. Here, in order to efficiently perform the photo-curing reaction of the photocurable resin layer or to improve the adhesion between the photocurable resin layer and the substrate, preliminary heating (pre-baking) may be performed as needed. The pre-baking can be carried out, for example, at 40 to 140 ° C for about 1 minute to 1 hour.

Then, in a state in which the support film is separated or the support film is peeled off, the mask is exposed and hardened by light having a wavelength of 190 to 500 nm. The reticle can be, for example, a hollowed out pattern. Further, the material of the photomask is preferably a light having a shielding wavelength of 190 to 500 nm, and for example, chromium or the like is preferably used, but is not limited thereto.

Light having a wavelength of 190 to 500 nm is, for example, light of various wavelengths generated by a radiation generating device, for example, ultraviolet light such as g-ray or i-ray, far-ultraviolet light (248 nm, 193 nm), or the like. The wavelength is preferably 248 to 436 nm. The exposure amount is preferably, for example, 10 to 3,000 mJ/cm ² . By exposure in the above manner, the exposed portions are crosslinked to form a pattern insoluble in a developer described later.

Further, in order to improve the development sensitivity, post-exposure heat treatment (PEB) is performed. The post-exposure heat treatment can be carried out, for example, at 40 to 140 ° C for 0.5 to 10 minutes.

It is then developed with a developing solution. The developer may be a solvent used in the preparation of a chemically amplified negative-type photoresist material used for forming a photocurable resin layer of the photocurable dry film of the present invention, using a 2.38% TMAH aqueous solution. For example, an alcohol such as isopropyl alcohol (IPA) or a ketone such as cyclohexanone is preferably a diol such as propylene glycol monomethyl ether or the like. The development can be carried out by a usual method, for example, by immersing the patterned substrate in a developing solution or the like. Thereafter, washing, rinsing, drying, and the like are carried out as needed to obtain a film of a photocurable resin layer having a desired pattern. Further, when it is not necessary to form a pattern, for example, when only a uniform film is desired, the remaining steps of not using the mask can be carried out in the same manner as described above for the pattern forming method.

Further, the obtained pattern may be post-hardened using an oven or a hot plate at a temperature of 100 to 250 ° C, preferably 150 to 220 ° C, and more preferably 170 to 190 ° C. When the post-hardening temperature is 100 to 250 ° C, the crosslinking density of the film of the photocurable resin layer can be increased, and the remaining volatile components can be removed, and the viewpoint of adhesion, heat resistance, strength, and electrical properties of the substrate can be considered. More ideal. The post-hardening time can be from 10 minutes to 10 hours.

The hardened film obtained in this manner is excellent in flexibility, adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance to the flux liquid, and such a hardened film is used as a semiconductor element for the protective film. Excellent reliability, especially to prevent cracking during temperature cycle test. In other words, the photocurable dry film of the present invention is suitable for protective films for electric and electronic parts, semiconductor elements, and the like.

The photocurable dry film of the present invention can be effectively used for a substrate having such a groove or a hole. Therefore, the present invention provides either or both of a groove and a hole having an opening width of 10 to 100 μm and a depth of 10 to 120 μm. The substrate is a laminate in which a cured layer of a photocurable resin formed of a photocurable dry film is laminated.

As described above, the chemically amplified negative-type photoresist material of the present invention and the photocurable dry film produced using the same are cured by curing, and have adhesion to substrates, heat resistance, electrical properties, A protective film having excellent mechanical strength and chemical resistance, and therefore, an insulating film for a semiconductor element, a multilayer printed circuit board insulating film, a solder resist mask, a surface coating film, and a tantalum substrate through wiring (TSV) for rewiring applications. The use of the buried insulating film is effective, and is effective for substrate bonding applications and the like. [Examples]

The present invention will be specifically described below by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples. Also, the following examples represent parts by mass.

I. Preparation of Chemical Amplified Negative Photoresist Material The chemical structural formula of the compound (M-1) to (M-12) used in the following synthesis examples is as follows. 【化86】

Further, the polymer compound containing a polyfluorene skeleton having a repeating unit represented by the following general formula (1), and a polymer compound having a polyfluorene skeleton having a repeating unit represented by the following formula (24) are as follows . 【化87】 (wherein R ¹ to R ⁴ , a, b, c, d, e, f, g, h, m, X, Y, W, and U are the same as described above.) (wherein R ²¹ to R ²⁴ , R ¹⁸ , R ¹⁹ , a', b', c', d', e', f', g', h', m', o, X', Y, W, and U are the same as before.)

[Synthesis Example 1] Synthesis of 4,4'-bis(4-hydroxy-3-allylphenyl)pentanol (M-1) In a 5 L flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, bisphenolic acid was added. 458 g, 884 g of potassium carbonate and 2000 g of dimethylacetamide were added to a stirred state at room temperature under a nitrogen atmosphere, and 774 g of bromopropene was added dropwise thereto, followed by stirring at 60 ° C for 58 hours. While maintaining the temperature, 221 g of potassium carbonate, 193 g of bromopropene and 500 g of dimethylacetamide were added, and the mixture was stirred at 60 ° C for 20 hours. 2000 g of water was added dropwise under ice cooling, and after the reaction was stopped, 1000 g of toluene, 1000 g of hexane, and 2000 g of water were added, and the organic layer was separated. The obtained organic layer was washed with water of 2000 g, water of 500 g for 4 times, and saturated brine of 500 g, and the solvent was distilled off to obtain 4,4-bis(4-allyloxyphenyl)pentane as a crude product. Acid allyl ester 686 g.

In a 5 L flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 655 g of allyl 4,4-bis(4-allyloxyphenyl)pentanoate and 1310 g of tetrahydrofuran were added under a nitrogen atmosphere to dissolve the solution. 605 g of sodium bis(2-methoxyethoxy)aluminum (70% by mass toluene solution) was hydrogenated under ice cooling. After stirring at room temperature for 3 hours, 1,526 g of a 10% by mass aqueous hydrochloric acid solution was added dropwise under ice cooling to stop the reaction. 250 g of ethyl acetate and 750 g of toluene were added to the reaction liquid, and the organic layer was separated and washed three times with 500 g of water. After the solvent of the obtained organic layer was distilled off, it was dissolved in 1,000 g of toluene, washed five times with 300 g of a 4% by mass aqueous sodium hydroxide solution, 330 g of a 2% by mass aqueous hydrochloric acid solution, and 300 g of water. Thereafter, the obtained organic layer was subjected to solvent distillation to obtain 555 g of 4,4-bis(4-allyloxyphenyl)pentanol as a crude material. Then, 500 g of 4,4-bis(4-allyloxyphenyl)pentanol and 500 g of N,N-diethylaniline were placed in a 5 L flask equipped with a stirrer, a thermometer, and a nitrogen substitution apparatus under a nitrogen atmosphere. It was dissolved, heated to 180 ° C, stirred for 18 hours, and then cooled to room temperature. After the ice-cooling, 1460 g of 10% by mass hydrochloric acid was added dropwise, and 2,400 g of ethyl acetate was added to the reaction mixture, and the organic layer was separated and washed 4 times with water (2400 g). After the solvent of the obtained organic layer was distilled off, 500 g of ethyl acetate was dissolved, and 2000 g of hexane was added dropwise with stirring. Thereafter, the hexane layer was removed, and the remaining oily substance was dissolved in ethyl acetate (500 g) and recovered, and the obtained organic layer was subjected to solvent distillation to obtain 4,4'-bis(4-hydroxy-3) in a yield of 93%. -Allylphenyl)pentanol (M-1) 466 g. Further, the compound (M-1) was identified by ¹ H-NMR (600 MHz) (JEOL-600 Japan Electronics).

[Synthesis Example 2] Synthesis of bis(4-hydroxy-3-allylphenyl)-(4-hydroxyphenyl)-methane (M-2) was weighed in a 1-L 3-neck flask which was replaced with nitrogen. 5-hydroxybenzaldehyde 50.0 g (409 mmol) and 2-allylphenol 330.0 g (2,457 mmol). After stirring at room temperature, and dissolving 4-hydroxybenzaldehyde, it was transferred to an ice bath, and 7.9 g of methanesulfonic acid was slowly added dropwise while maintaining the reaction liquid at 10 ° C or lower. After completion of the dropwise addition, the mixture was aged at room temperature for 10 hours, and then 400 g of toluene and 400 g of a saturated aqueous sodium hydrogencarbonate solution were added, and the mixture was transferred to a 2 L separatory funnel. The aqueous layer was removed, and 400 g of a saturated aqueous sodium hydrogencarbonate solution was added thereto to carry out a liquid separation operation, and then the mixture was washed twice with 400 g of ultrapure water. The organic layer taken out was crystallized by 4400 g of hexane, and the supernatant was removed, and the residue was dissolved in 300 g of toluene, followed by crystallization from 2000 g of hexane. This operation was repeated once more, and the precipitated crystals were separated by filtration and dried to give bis(4-hydroxy-3-allylphenyl)-(4-hydroxyphenyl)-methane (M-2) 95 g. 58%. Further, the compound (M-2) was identified by ¹ H-NMR (600 MHz) (JEOL-600 Japan Electronics).

[Synthesis Example 3] Synthesis of 3,3'-diallyl-4,4'-dihydroxy-1,1'-biphenyl (M-3) in a 3L with a stirrer, a thermometer, and a nitrogen substitution device 300 g of 4,4'-biphenol, 534 g of potassium carbonate and 1200 g of acetone were added to the flask, and 468 g of bromopropene was added dropwise thereto under stirring in a nitrogen atmosphere at room temperature, followed by stirring at 50 ° C for 24 hours. After cooling to room temperature, 1200 g of water was added to terminate the reaction, and the precipitated crystals were separated by filtration. Further, the obtained crystal was washed three times with 1200 g of water, and the solvent was distilled off to obtain 429 g of 4,4'-bis(allyloxy)-1,1'-biphenyl as a crude material.

Then, 4,4'-bis(allyloxy)-1,1'-biphenyl 429 g, N, N-diethyl was added to a 3 L flask equipped with a stirrer, a thermometer, and a nitrogen substitution device under a nitrogen atmosphere. The aniline was dissolved in 858 g, heated to 180 ° C, stirred for 24 hours, and then cooled to room temperature. 2300 g of 10% by mass hydrochloric acid was added dropwise under ice cooling, and 1500 g of ethyl acetate was added to the reaction mixture, and the organic layer was separated and washed with water 1500 g 5 times. After the solvent of the obtained organic layer was distilled off, 93 g of ethyl acetate and 2800 g of hexane were added, and the mixture was stirred at room temperature for a period of time to precipitate crystals, and the crystals were separated by filtration. Thereafter, it was washed twice with 1000 g of hexane to obtain 370 g of 3,3'-diallyl-4,4'-dihydroxy-1,1'-biphenyl (M-3) in a yield of 86% in 2 steps. Further, the compound (M-3) was identified by ¹ H-NMR (600 MHz) (JEOL-600 Japan Electronics).

[Synthesis Example 4] Synthesis of Compound (M-12) 3.4 g (3.28 mol) of dimethoxymethyl decane and toluene of chloroplatinic acid were weighed in a 1-liter 3-neck flask equipped with a stirrer, a thermometer, and a nitrogen substitution apparatus. The solution (5 mass%) was 2.1 g and heated to 60 °C. 400 g (2.98 mol) of 4-methoxystyrene was added dropwise thereto over 7 hours. At this time, as the internal temperature of the reaction system rises, the heating temperature also rises to 100 °C. After completion of the dropwise addition, the mixture was cooled to room temperature, and subjected to distillation purification to obtain 583 g of a compound (M-12), yield: 81.4%. Further, the compound (M-12) was identified by ¹ H-NMR (600 MHz) (JEOL-600 Japan Electronics).

[Synthesis Example 5] Synthesis of Compound (M-9) Into a 1-L three-necked flask, 212 g of the compound (M-12) was weighed, and 162 g of a 7.5% by mass aqueous potassium hydroxide solution was added thereto while stirring at room temperature. After the input was heated to 100 ° C, the produced methanol was taken out from the system and matured for 6 hours. After cooling to room temperature, 200 g of toluene and 68 g of 10 mass% hydrochloric acid were added, and the mixture was transferred to a 1 L separatory funnel to remove the lower aqueous layer. Further, the mixture was washed three times with 50 g of ultrapure water, and the organic layer was concentrated under reduced pressure to give 166 g of the compound (M-12).

164 g of the obtained hydrolysis condensate was weighed in a 1-L 3-neck flask substituted with nitrogen (0.84 mol if a unit of condensation is assumed to be its molecular weight), and 125 g of a cyclic tetramer of dimethyloxane ( If 1 unit of condensation is assumed to be its molecular weight, it is 1.69 mol) and 1,1,3,3-tetramethyldioxane 37.4 g (0.28 mol), and stirred at room temperature. 1.5 g of trifluoromethanesulfonic acid was added dropwise with stirring, and after the completion of the dropwise addition, the mixture was heated to 60 ° C and aged for 3 hours. After cooling to room temperature, 300 g of toluene and 208 g of a 4% by mass aqueous sodium hydrogencarbonate solution were added, and the mixture was stirred for 1 hour. The mixture was transferred to a 1 L separatory funnel, and the lower aqueous layer was removed, and the mixture was washed twice with 200 g of ultrapure water. The organic layer was concentrated under reduced pressure to give Compound (M-9). Further, the compound (M-9) was identified by ¹ H-NMR (600 MHz) (JEOL-600 Japan Electronics).

[Synthesis Example 6] The polymer compound (A-1) containing a polyfluorene skeleton was synthesized in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, and 120 g of the compound (M-1) was dissolved. After 350 g of toluene, 39 g of the compound (M-3) and 85 g of the compound (M-7) were added, and the mixture was heated to 60 °C. Thereafter, 1.1 g of a platinum-carrying catalyst (5 mass%) was placed on the carbon, and the mixture was heated to 90 ° C and aged for 3 hours. Further, the mixture was cooled to 60 ° C, and 1.1 g of a platinum-supporting catalyst (5 mass%) was charged, and 62 g of the compound (M-11) was added dropwise to the flask over a period of 30 minutes. At this time, the temperature inside the flask was raised to 65 to 67 °C. After completion of the dropwise addition, the mixture was aged at 90 ° C for 3 hours, and after cooling to room temperature, 780 g of methyl isobutyl ketone was added to the reaction liquid, and the reaction solution was filtered under pressure with a filter to remove a platinum catalyst. Further, 780 g of pure water was added to the obtained polymer compound solution containing a polyfluorene skeleton, and the mixture was stirred and allowed to stand for liquid separation to remove the aqueous layer of the lower layer. This liquid separation washing operation was repeated 6 times to remove a trace amount of the acid component in the polymer compound solution containing the polyfluorene skeleton. The solvent in the polymer compound solution containing the polyoxygen skeleton was distilled off under reduced pressure, and 750 g of tetrahydrofuran was added thereto, followed by concentration under reduced pressure to obtain a tetrahydrofuran solution having a solid concentration of 30% by mass.

Then, in a flask of 3 L equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 1,000 g of a 30 mass% tetrahydrofuran solution containing the above polymerized polysiloxane skeleton was placed, and 31 g of succinic anhydride and 32 g of triethylamine were added. , warm to 50 ° C. After stirring for 2 hours, it was cooled to room temperature, and 900 g of a saturated aqueous solution of ammonium chloride and 1,500 g of ethyl acetate were added to terminate the reaction. Thereafter, the water layer was removed, and the liquid separation washing operation was repeated 5 times with 900 g of ultrapure water. The solvent in the organic layer to be taken out was distilled off under reduced pressure, and 600 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 40 to 50% by mass, thereby obtaining cyclopentanone as a main solvent. A solution of a polymer compound (A-1) containing a polyoxonium skeleton containing a carboxylic acid. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and as a result, the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.513, h' = 0.187. X' and U are as follows. 【化89】

[Synthesis Example 7] The synthesis of the polymer compound (A-2) containing a polyfluorene skeleton was carried out in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, and 120 g of the compound (M-1) was dissolved. After 497 g of toluene, 91 g of the compound (M-3) and 119 g of the compound (M-7) were added, and the mixture was heated to 60 °C. Thereafter, 1.6 g of a platinum catalyst (5 mass%) was charged on the carbon, and the mixture was heated to 90 ° C, and aged for 3 hours. The mixture was further cooled to 60 ° C, and 1.6 g of a platinum-supporting catalyst (5 mass%) was charged, and 87 g of the compound (M-11) was added dropwise to the flask over a period of 30 minutes. At this time, the temperature inside the flask was raised to 65 to 67 °C. After completion of the dropwise addition, the mixture was aged at 90 ° C for 3 hours, and after cooling to room temperature, 780 g of methyl isobutyl ketone was added to the reaction liquid, and the reaction solution was filtered under pressure with a filter to remove a platinum catalyst. Further, 780 g of pure water was added to the obtained polymer compound solution containing a polyfluorene skeleton, and the mixture was stirred and allowed to stand for liquid separation to remove the aqueous layer of the lower layer. This liquid separation washing operation was repeated 6 times to remove a trace amount of the acid component in the polymer compound solution containing the polyfluorene skeleton. The solvent in the polymer compound solution containing the polyoxygen skeleton was distilled off under reduced pressure, and 1,078 g of tetrahydrofuran was added thereto, followed by concentration under reduced pressure to obtain a tetrahydrofuran solution having a solid concentration of 30% by mass.

Then, 1,400 g of a 30 mass% tetrahydrofuran solution containing the above polymerized polysiloxane skeleton was placed in a flask equipped with a stirrer, a thermometer, a nitrogen gas replacement device, and a reflux condenser, and 31 g of succinic anhydride and 32 g of triethylamine were added. , heat up to 50 ° C. After stirring for 2 hours, it was cooled to room temperature, and 900 g of a saturated aqueous solution of ammonium chloride and 1,500 g of ethyl acetate were added to terminate the reaction. Thereafter, the water layer was removed, and the liquid washing operation was repeated 5 times with 900 g of ultrapure water. The solvent in the organic layer to be taken out was distilled off under reduced pressure, and 600 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid concentration of 40 to 50% by mass to obtain a cyclopentanone as a main solvent. A solution of a polymer compound (A-2) containing a polyoxyxylene skeleton containing a carboxylic acid. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 13,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.367, b' = 0.133, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.367, h' = 0.133. X' and U are as follows. 【化90】

[Synthesis Example 8] Synthesis of a polymer compound (A-3) containing a polyfluorene skeleton: 85 g of the compound (M-7) of Synthesis Example 6 was replaced with 362 g of the compound (M-8), and the same formulation was used to synthesize a poly A polymer compound of a ruthenium skeleton is added with cyclopentanone as a main solvent, and a solution containing the polymer compound (A-3) containing a polyfluorene skeleton is obtained. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyoxygen skeleton is measured by GPC, and the weight average molecular weight is 30,000 in terms of polystyrene. Further, in the above formula (24), a'=0.220, b'=0.080, c'=0, d'=0, e'=0, f'=0, g'=0.513, h'=0.187, . X' and U are as follows. 【化91】

[Synthesis Example 9] Synthesis of polymer compound (A-4) containing a polyfluorene skeleton: 85 g of the compound (M-7) of Synthesis Example 6 was replaced with 188 g of the compound (M-9), and the same formulation was used to synthesize a poly A polymer compound of a ruthenium skeleton is added with cyclopentanone as a main solvent, and a solution containing the polymer compound (A-4) containing a polyfluorene skeleton is obtained. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 26,000 in terms of polystyrene. Further, in the above formula (24), a'=0.220, b'=0.080, c'=0, d'=0, e'=0, f'=0, g'=0.513, h'=0.187, . X' and U are as follows. 【化92】

[Synthesis Example 10] Synthesis of polymer compound (A-5) containing a polyfluorene skeleton: 85 g of the compound (M-7) of Synthesis Example 6 was replaced with 141 g of the compound (M-10), and the same formulation was used to synthesize a poly A polymer compound of a ruthenium skeleton is added with cyclopentanone as a main solvent, and a solution containing the polymer compound (A-5) containing a polyfluorene skeleton is obtained. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyoxygen skeleton is measured by GPC, and the weight average molecular weight is 10,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.513, h' = 0.187. X' and U are as follows. 【化93】

[Synthesis Example 11] The synthesis of the polymer compound (A-6) containing a polyfluorene skeleton was carried out in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, and 120 g of the compound (M-1) was dissolved. After 411 g of toluene, 45 g of the compound (M-3), 24 g of the compound (M-4), and 219 g of the compound (M-9) were added, and the mixture was heated to 60 °C. Thereafter, 1.3 g of a platinum catalyst (5 mass%) was placed on the carbon, and the mixture was heated to 90 ° C, and aged for 3 hours. Further, the mixture was cooled to 60 ° C, and 1.3 g of a platinum-supporting catalyst (5 mass%) was charged on the carbon, and 73 g of the compound (M-11) was added dropwise to the flask over a period of 30 minutes. At this time, the temperature inside the flask was raised to 65 to 67 °C. After completion of the dropwise addition, the mixture was aged at 90 ° C for 3 hours, and after cooling to room temperature, 780 g of methyl isobutyl ketone was added to the reaction liquid, and the reaction solution was filtered under pressure with a filter to remove a platinum catalyst. Further, 780 g of pure water was added to the obtained polymer compound solution containing a polyfluorene skeleton, and the mixture was stirred and allowed to stand for liquid separation to remove the aqueous layer of the lower layer. This liquid separation washing operation was repeated 6 times to remove a trace amount of the acid component in the polymer compound solution containing the polyfluorene skeleton. The solvent in the polymer compound solution containing the polyfluorene skeleton was distilled off under reduced pressure, and 1,050 g of tetrahydrofuran was added thereto, followed by concentration under reduced pressure to a tetrahydrofuran solution having a solid concentration of 30% by mass.

Then, 1,500 g of a tetrahydrofuran solution containing 30% by mass of the polymer compound containing a polyfluorene skeleton was placed in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen gas substitute, and a reflux condenser, and 31 g of succinic anhydride and 32 g of triethylamine were added thereto to raise the temperature. To 50 ° C. After stirring for 2 hours, it was cooled to room temperature, and 900 g of a saturated aqueous solution of ammonium chloride and 1,500 g of ethyl acetate were added to terminate the reaction. Thereafter, the water layer was removed, and the liquid-washing operation was repeated five times with 900 g of ultrapure water. The solvent in the organic layer to be taken out is distilled off under reduced pressure, and 600 g of cyclopentanone is added, and then concentrated under reduced pressure to a cyclopentanone solution having a solid concentration of 40 to 50% by mass to obtain a carboxylic acid containing cyclopentanone as a main solvent. A solution of the polymer compound (A-6) containing a polyoxygen skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyoxygen skeleton was measured by GPC, and the weight average molecular weight was 24,000 in terms of polystyrene. Further, in the above formula (1), a = 0.293, b = 0.107, c = 0, d = 0, e = 0, f = 0, g = 0.440, h = 0.160. X and U are as follows. 【化94】

[Synthesis Example 12] Synthesis of polymer compound (A-7) containing a polyfluorene skeleton The same formulation was used except that 24 g of the compound (M-4) of Synthesis Example 11 was replaced with 17 g of the compound (M-5). A polymer compound containing a polyfluorene skeleton is synthesized, and cyclopentanone is added as a main solvent to obtain a solution containing the polymer compound (A-7) containing a polyfluorene skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 23,000 in terms of polystyrene. Further, in the above formula (1), a = 0.293, b = 0.107, c = 0, d = 0, e = 0, f = 0, g = 0.440, h = 0.160. X and U are as follows. 【化95】

[Synthesis Example 13] Synthesis of polymer compound (A-8) containing a polyfluorene skeleton The same formulation was used except that 24 g of the compound (M-4) of Synthesis Example 11 was replaced with 24 g of the compound (M-6). A polymer compound containing a polyfluorene skeleton is synthesized, and cyclopentanone is added as a main solvent to obtain a solution containing the polymer compound (A-8) containing a polyfluorene skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 23,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0.073, d' = 0.027, e' = 0, f' = 0, g' = 0.440, h' = 0.160. X', Y and U are as follows. 【化96】

[Synthesis Example 14] Synthesis of polymer compound (A-9) containing a polyfluorene skeleton The same formulation was carried out except that 120 g of the compound (M-1) of Synthesis Example 6 was replaced with 131 g of the compound (M-2). A polymer compound containing a polyfluorene skeleton is synthesized, and cyclopentanone is added as a main solvent to obtain a solution containing the polymer compound (A-9) containing a polyfluorene skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.513, h' = 0.187. X' and U are as follows. 【化97】

[Synthesis Example 15] Synthesis of polymer compound (A-10) containing a polyfluorene skeleton: 31 g of succinic anhydride of Synthesis Example 6 was replaced with 48 g of cyclohexyldicarboxylic anhydride, and the same formulation was used to synthesize polyoxyl oxide. A polymer compound of a skeleton, to which cyclopentanone is added as a main solvent, a solution containing a polymer compound (A-10) containing a polyfluorene skeleton is obtained. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.513, h' = 0.187. X' and U are as follows. 【化98】

[Synthesis Example 16] Synthesis of polymer compound (A-11) containing a polyfluorene skeleton: 31 g of succinic anhydride of Synthesis Example 6 was replaced with 51 g of 5-northene-2,3-dicarboxylic anhydride, and the like In the same formulation, a polymer compound containing a polyfluorene skeleton was synthesized, and cyclopentanone was added as a main solvent to obtain a solution containing the polymer compound (A-11) containing a polyfluorene skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (24), a' = 0.220, b' = 0.080, c' = 0, d' = 0, e' = 0, f' = 0, g' = 0.513, h' = 0.187. X' and U are as follows. 【化99】

[Synthesis Example 17] The synthesis of the polymer compound (A-12) containing a polyfluorene skeleton was carried out in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, and 171 g of the compound (M-1) was dissolved. After 350 g of toluene, 85 g of the compound (M-7) was added, and the mixture was heated to 60 °C. Thereafter, 1.1 g of a platinum-carrying catalyst (5 mass%) was placed on the carbon, and the mixture was heated to 90 ° C and aged for 3 hours. Further, the mixture was cooled to 60 ° C, and 1.1 g of a platinum-supporting catalyst (5 mass%) was charged, and 62 g of the compound (M-11) was added dropwise to the flask over a period of 30 minutes. At this time, the temperature inside the flask was raised to 65 to 67 °C. After completion of the dropwise addition, the mixture was aged at 90 ° C for 3 hours, and after cooling to room temperature, 780 g of methyl isobutyl ketone was added to the reaction liquid, and the reaction solution was filtered under pressure with a filter to remove a platinum catalyst. Further, 780 g of pure water was added to the obtained polymer compound solution containing a polyfluorene skeleton, and the mixture was stirred and allowed to stand for liquid separation to remove the aqueous layer of the lower layer. This liquid separation washing operation was repeated 6 times to remove a trace amount of the acid component in the polymer compound solution containing the polyfluorene skeleton. The solvent in the polymer compound solution containing the polyfluorene skeleton was distilled off under reduced pressure, and 750 g of tetrahydrofuran was added thereto, followed by concentration under reduced pressure to a tetrahydrofuran solution having a solid concentration of 30% by mass.

Then, in a 3 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 1,000 g of a 30% by mass solution of a polymer compound containing a polyfluorene skeleton and a tetrahydrofuran solution were added thereto, and 32 g of succinic anhydride and 33 g of triethylamine were added thereto. Warm to 50 ° C. After stirring for 2 hours, it was cooled to room temperature, and 900 g of a saturated aqueous solution of ammonium chloride and 1,500 g of ethyl acetate were added to terminate the reaction. Thereafter, the water layer was removed, and the liquid separation washing operation was repeated 5 times with 900 g of ultrapure water. The solvent in the organic layer to be taken out is distilled off under reduced pressure, and 600 g of cyclopentanone is added thereto, and then concentrated under reduced pressure to a cyclopentanone solution having a solid concentration of 40 to 50% by mass to obtain a cyclopentanone as a main solvent. A solution of a polymer compound (A-12) containing a polyoxyxylene skeleton of a carboxylic acid. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (1), a=0, b=0, c=0, d=0, e=0.220, f=0.080, g=0.513, h=0.187. W and U are as follows. 【化100】

[Synthesis Example 18] Synthesis of a polymer compound (A-13) containing a polyfluorene skeleton: 32 g of succinic anhydride used in Synthesis Example 17 and 33 g of triethylamine were each replaced with 46 g of succinic anhydride and 46 g of triethylamine. A polymer compound containing a polyfluorene skeleton was synthesized in the same manner, and cyclopentanone was added as a main solvent to obtain a solution containing the polymer compound (A-13) containing a polyfluorene skeleton. The molecular weight of the polymer compound containing a polyfluorene skeleton in the polymer compound solution containing the polyfluorene skeleton was measured by GPC, and the weight average molecular weight was 10,000 in terms of polystyrene. Further, in the above formula (1), a = 0, b = 0, c = 0, d = 0, e = 0, f = 0, g = 0.733, and h = 0.267. U is as follows. 【化101】

Using the solution of the polymer compound (A-1 to A-13) containing the polyfluorene skeleton synthesized in the above Synthesis Examples 6 to 18, the crosslinking agent and the photoacid generator were blended in the composition and blending amount described in Table 1. Further, a basic compound was blended, and cyclopentanone was blended as an additional solvent to prepare a photoresist material having a resin content of 45 mass%. After that, the mixture was stirred, mixed, and dissolved, and then subjected to precision filtration using a 0.5 μm filter made of Teflon (registered trademark) to obtain a photoresist.

【Table 1】

Further, XL-2 described in Table 1 is EOCN-1020-55 (manufactured by Nippon Kayaku Co., Ltd.), photoacid generator (PAG-1), crosslinking agent (XL-1), and basic compound (Amine-). 1) as follows. 【化102】

II. Exposure and pattern formation After the above-mentioned photoresist materials 1 to 13 were dispensed to 5 mL on a ruthenium substrate, the substrate was rotated, that is, coated by a spin coating method to have a film thickness of 20 μm. Then, prebaking was performed on a hot plate at 100 ° C for 2 minutes. Then, using a mask aligner (product name: MA-8) made of Suss microtek, a mask capable of forming a hole of 20 μm in a 1:1 orientation was attached, and exposure of wide-band light was applied. After the exposure, the substrate was heated at 110 ° C for 2 minutes (PEB) and then cooled. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for 1 minute to carry out patterning. The obtained pattern on the substrate was then post-hardened by blowing nitrogen at 180 ° C for 2 hours. Similarly, the ruthenium substrate was replaced, and the ruthenium substrate was also patterned on the copper substrate.

Then, each substrate was cut out so that the shape of the obtained hole pattern was observed, and the shape of the hole pattern was observed using a scanning electron microscope (SEM). The aperture of the hole pattern was processed to an optimum exposure amount (exposure amount in terms of 365 nm light) having the same size as the mask size of 20 μm. Further, the shape of the observation is shown in Table 2.

【Table 2】

As shown in Table 2, when the photoresist materials 1 to 13 containing the polymer compound containing the polyfluorene skeleton of the present invention were used and patterned by using 2.38% aqueous solution of tetramethylammonium hydroxide, on the substrate, No significant pattern peeling occurred on the tantalum nitride substrate or on the copper substrate, and a good pattern shape was obtained.

III. Production of Photocurable Dry Film For the photocurable dry film, the polymer compound (A-1 to A-13) containing a polyfluorene skeleton synthesized in Synthesis Examples 6 to 18 as described above is used. The solution is not blended with cyclopentanone as a solvent, and the crosslinking agent, the photoacid generator, and the basic compound are blended with the composition and the amount of the mixture described in Table 1 in the same manner as above, followed by stirring, mixing, and After the solution was dissolved, a 1.0 μm filter made of Teflon (registered trademark) was used for precision filtration to obtain a photoresist material 1' to 13'.

Using a die coater as a film coater, using a polyethylene terephthalate film (thickness: 38 μm) as a support film, the photoresist materials 1' to 13' were coated on the support film at a coating thickness of 50 μm. . Then, it was passed through a hot air circulating oven (length 4 m) set at 100 ° C for 5 minutes to form a photocurable resin layer on the support film. In addition, a polyethylene film (thickness: 50 μm) as a protective film was bonded to the photocurable resin layer at a pressure of 1 MPa using a laminating roll to form photocurable dry films 1 to 13. Further, the film thickness of the photocurable resin layer was 50 μm. An example of a film is shown in Table 3 as an example.

IV. Exposure and pattern formation The protective film of the photocurable dry film 1 to 13 obtained in the above manner was peeled off, and a vacuum laminator (product name: TEAM-100RF) manufactured by Takatori Co., Ltd. was used, and a vacuum chamber was set. The photocurable resin layer on the support film was adhered to the tantalum substrate at a vacuum of 100 Pa at a temperature of 100 °C. After returning to normal pressure, the substrate was cooled to 25 ° C, taken out from the vacuum laminator, and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Next, using a mask aligning machine made by Sussmicrotek (product name: MA-8), a mask capable of forming a hole of 40 μm in a vertical and horizontal 1:1 arrangement was applied, and exposure of a wide-band light was applied. After the exposure, the substrate was heated at 130 ° C for 5 minutes (PEB) and then cooled. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for 1 minute to carry out patterning. The obtained pattern on the substrate was then post-hardened by blowing nitrogen at 180 ° C for 2 hours. Similarly, the tantalum substrate was replaced, and the photocurable dry films 1 to 13 produced in the above manner were laminated on a tantalum nitride substrate and a copper substrate, and then patterned.

Then, each substrate was cut out so that the shape of the obtained hole pattern was observed, and the shape of the hole pattern was observed using a scanning electron microscope (SEM). The aperture of the hole pattern was processed to an optimum exposure amount (exposure amount in terms of 365 nm light) having the same size as the mask size of 40 μm. Further, the shape of the observation is shown in Table 3.

【table 3】

When the photocurable dry films 1 to 13 containing the photocurable resin composition containing the polymer compound of the polyfluorene skeleton of the present invention are patterned, they are patterned on a tantalum substrate or a tantalum nitride substrate. No significant pattern peeling occurred on the copper substrate, and a good pattern shape was obtained.

V. Landfill performance It is prepared to form 200 吋 (150 mm) 矽 wafers having a circular opening having a circular opening diameter of 10 to 100 μm (interval 10 μm) and a depth of 10 to 120 μm (interval 10 μm). The protective film of the photocurable dry film 1 to 5 and the photocurable dry film 12 was peeled off, and a vacuum laminator (product name: TEAM-100RF) manufactured by Takatori Co., Ltd. was used, and the vacuum chamber was set to a vacuum of 100 Pa. The photocurable resin layer on the support film was adhered to the substrate at a temperature of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C, taken out from the vacuum laminator, and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Then, a mask alignment machine (product name: MA-8) manufactured by Sussmicrotek Co., Ltd. was used, and the substrate was irradiated with wide-band light at the exposure amount (wavelength 365 nm) shown in Table 4. After the exposure, the substrate was heated at 110 ° C for 5 minutes (PEB) and then cooled. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for 1 minute to carry out patterning. The obtained pattern on the substrate was then post-hardened by blowing nitrogen at 180 ° C for 2 hours. Further, the obtained substrate was cut, the cross section of the circular hole was exposed, and the cross section of the circular hole was observed using a scanning electron microscope (SEM), and it was evaluated whether or not there was a defect. The results are shown in Table 4.

【Table 4】

As shown in Table 4, the round holes of the tantalum wafer in which the photocurable dry film of the present invention was adhered were filled without defects, and it was judged that the film for electrical and electronic component protection was excellent in landfill performance.

VI. Electrical properties (insulation breaking strength) The protective film of the photocurable dry film 1 to 5 and the photocurable dry film 12 having a film thickness of 50 μm is peeled off, and the photocurable resin layer on the support film is exposed to a temperature of 100 ° C. The conditions are in close contact with the substrate specified in JIS K 6249. Then, the substrate was cooled to room temperature and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Further, a wide-band light having an exposure amount of 1,000 mJ/cm ² (wavelength: 365 nm) was irradiated onto the substrate by a quartz mask, using the above-described mask aligning machine. Then, the substrate was heated at 110 ° C for 5 minutes (PEB) and cooled. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for one minute. Then, nitrogen was blown in an oven at 180 for 2 hours and then post-hardened to prepare a substrate for measuring the dielectric breakdown strength. Then, the dielectric breakdown strength was measured in accordance with the measurement method specified in JIS K 6249. The results are shown in Table 5.

VII. Adhesiveness The protective film of the photocurable dry film 1 to 5 and the photocurable dry film 12 having a thickness of 50 μm was peeled off, and the vacuum chamber was used to have a vacuum of 100 Pa at 100 ° C using a vacuum laminator. The temperature condition causes the photocurable resin layer on the support film to be adhered to the untreated 6 直径 (150 mm) 矽 wafer. After returning to normal pressure, the substrate was cooled to 25 ° C, taken out from the vacuum laminator and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Then, using the above-described mask aligning machine, wide-band light having an exposure amount of 1,000 mJ/cm ² (wavelength: 365 nm) was irradiated to the substrate through a quartz reticle. The substrate was then heated at 110 ° C for 5 minutes (PEB) and cooled. Thereafter, nitrogen was blown at 180 ° C for 2 hours and then post-hardened using an oven to obtain a wafer with a hardened film.

The wafer was cut out into a square of 1 x 1 cm. Then use a special fixture to mount the aluminum pin with epoxy adhesive on the cut wafer. Thereafter, it was heated at 150 ° C for 1 hour using an oven to adhere the aluminum pin to the substrate. After cooling to room temperature, the initial adhesion was evaluated by using a film adhesion strength measuring device (Sebastian Five-A). The measurement conditions were such that the measurement speed was 0.2 kg/sec. Fig. 1 is an explanatory view showing a method of measuring adhesion. Further, Fig. 1 denotes a tantalum wafer (substrate), 2 denotes a hardened film, 3 denotes an aluminum pin with an adhesive, 4 denotes a support table, 5 denotes a gripping portion, and 6 denotes a stretching direction. The obtained number is the average enthalpy measured at 12 points, and the higher the number, the higher the adhesion of the hardened film to the substrate. The adhesion was evaluated by comparing the number obtained. The results are shown in Table 5.

VIII. Crack resistance The protective film of the photocurable dry film 1 to 5 having a film thickness of 50 μm and the photocurable dry film 12 was peeled off, and the vacuum chamber was used to have a vacuum of 100 Pa at 100 ° C using the vacuum laminator. The temperature condition causes the photocurable resin layer on the support film to adhere to the substrate used for the above test for the landfill property. After returning to normal pressure, the substrate was cooled to 25 ° C, taken out from the above vacuum laminator, and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Then, using the above-described mask aligning machine, a wide-band light having an exposure amount of 1,000 mJ/cm ² (wavelength: 365 nm) was irradiated to the substrate through a quartz mask. Then, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for one minute. Then, using an oven, nitrogen was blown at 180 ° C for 2 hours while post-hardening was performed. The substrate on which the hardened film was formed was placed in a temperature cycle tester having a cycle of -55 to +150 ° C, and it was investigated for whether or not cracks occurred in the hardened film up to 1,000 cycles. The results are shown in Table 5.

IX. Peeling liquid resistance The protective film of the photocurable dry film 1 to 5 and the photocurable dry film 12 having a film thickness of 50 μm was peeled off, and the vacuum chamber was set to a vacuum degree of 100 Pa using the vacuum laminator. The temperature condition of °C causes the photocurable resin layer on the support film to be adhered to the untreated 6 直径 (150 mm) 矽 wafer. After returning to normal pressure, the substrate was cooled to 25 ° C, taken out from the above vacuum laminator, and the support film was peeled off. After the support film was peeled off, it was prebaked on a hot plate at 100 ° C for 5 minutes. Then, the substrate was irradiated with a broadband light having an exposure amount of 1,000 mJ/cm ² (wavelength: 365 nm) through a mask made of quartz using the above-described mask aligning machine. The substrate was then heated at 110 ° C for 5 minutes (PEB) and cooled. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used as a developing solution, and three times of immersion development was performed for one minute. Then, nitrogen was blown at 180 ° C for 2 hours using an oven, and post-hardening was simultaneously performed to obtain a square pattern hardened film of 15 mm × 15 mm. Then, the substrate was immersed in NMP (N-methylpyrrolidone) at room temperature for 1 hour, and then the change in appearance and film thickness was examined, and the peeling liquid resistance was evaluated. The results are shown in Table 5.

【table 5】

As shown in Table 5, the cured film of the pattern was formed by using the photocurable dry film of the present invention, and the electrical properties, adhesion, crack resistance, and peeling liquid resistance of the film for electric/electronic component protection were good.

The present invention is not limited to the above embodiment. The above-described embodiments are exemplified and have substantially the same configuration and the same effects as those described in the claims of the present invention are included in the technical scope of the present invention.

【Symbol Description】
1‧‧‧矽 wafer (substrate)
2‧‧‧ hardened membrane
3‧‧‧Aluminum pin with adhesive
4‧‧‧Support desk
5‧‧‧ Grasping Department
6‧‧‧Stretching direction

Fig. 1 is a view showing the method of measuring the adhesion of the examples.

no

Claims (19)

a polymer compound containing a polyfluorene skeleton, characterized by having a repeating unit represented by the following formula (1) and having a weight average molecular weight of 3,000 to 500,000; In the formula, R ¹ to R ⁴ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be different or identical to each other; m is an integer of 1 to 100; a, b, c, and d are 0, e, and f Is 0 or a positive number, g and h are positive numbers; only a+b+c+d+e+f+g+h=1; further, X is a divalent organic group represented by the following formula (2), Y is The divalent organic group represented by the following formula (3), W is a divalent organic group represented by the following formula (4), and U is a divalent organic group represented by the following formula (5); Wherein Z is selected from the group consisting of divalent organic groups of any of the following; , the dotted line represents a bond, n is 0 or 1; R ⁵ and R ^{6 are} each a C 1~4 alkyl or alkoxy group, which may be the same or different; x is 0, 1, and 2 One; Wherein V is selected from the group consisting of divalent organic groups of any of the following; , the dotted line represents a bond, p is 0 or 1; R ⁷ and R ^{8 are} each a C 1~4 alkyl or alkoxy group, which may be the same or different; y is 0, 1, and 2 One; [chemical 6] Wherein the dotted line represents a bond, and T represents an alkylene group having 1 to 10 carbon atoms or a divalent aromatic group having 6 or 10 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group; Wherein the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group represented by the following formula (6); In the formula, the dotted line represents a bond, and R ¹¹ to R ¹⁴ are each a different or the same substituent, and represent a hydrogen atom, a halogen atom, a linear one having a carbon number of 1 to 12, a branched, a cyclic alkyl group, and a carbon. The aromatic group of 6 or 10, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may each be bonded to form a substituted or unsubstituted cyclic structure having 3 to 12 carbon atoms; j is any of 1 to 7 One. The polymer compound containing a polyxanylene skeleton according to the first aspect of the patent application, wherein a in the formula (1) is a=0, b is b=0, c is c=0, and d is d= 0, e is 0≦e≦0.8, f is 0≦f≦0.5, g is 0<g≦0.8, and h is 0<h≦0.5. The polymer compound containing a polyxanylene skeleton according to claim 1 or 2, wherein a in the formula (1) is a=0, b is b=0, and c is c=0, d is d=0, e is 0≦e≦0.3, f is 0≦f≦0.2, g is 0<g≦0.8, and h is 0<h≦0.5. A method for producing a polymer compound containing a polyfluorene skeleton, which is a method for producing a polymer compound containing a polyfluorene skeleton according to any one of claims 1 to 3, which is characterized in that it has the following All or a part of the alcoholic or phenolic hydroxyl group of the polymer compound containing the polyoxynium skeleton represented by the formula (7) is reacted with a dicarboxylic anhydride to introduce a carboxyl group; Wherein R ¹ to R ⁴ , a, b, c, d, m, X, Y, and W are the same as defined above; k and l are positive numbers, k=e+g, l=f+h; , f, g, and h are the same as above. The method for producing a polymer compound containing a polyfluorene skeleton according to the fourth aspect of the invention, wherein the hydroquinone represented by the following structural formula (8) and the dihydroorganoindene represented by the following formula (9) are used. Any one or both of oxane, a phenol compound having 2 allyl groups represented by the following formula (10), and a compound having 2 allyl groups represented by the following formula (11) Or both, and a phenol compound having two allyl groups represented by the following formula (12), which is polymerized in the presence of a catalyst, and is obtained as a polyfluorene skeleton represented by the formula (7). Molecular compound Wherein R ³ , R ⁴ , and m are the same as defined above; Wherein Z, R ⁵ , R ⁶ , n, and x are the same as above; [Chemical 13] Wherein V, R ⁷ , R ⁸ , p, and y are the same as defined above; Wherein T and R ^{9 are the} same as defined above. The method for producing a polymer compound containing a polyfluorene skeleton according to the fifth aspect of the invention, wherein a compound represented by the following formula (13) is used as the phenol having two allyl groups represented by the formula (12) Compound In the formula, R ^{9 is the} same as the above, and s is a positive number of 1 to 12. The method for producing a polymer compound containing a polyfluorene skeleton according to the fifth aspect of the invention, wherein a compound represented by the following formula (14) is used as the phenol having two allyl groups represented by the formula (12) Compound Wherein R ^{9 is the} same as defined above. a polymer compound containing a polyfluorene skeleton, characterized by having a repeating unit represented by the following formula (24) and having a weight average molecular weight of 3,000 to 500,000; In the formula, R ²¹ to R ²⁴ may be different or the same, and represent a monovalent organic group having 1 to 15 carbon atoms, and may also contain an oxygen atom; and R ¹⁸ is a hydroxyl group or alkoxy group represented by the following formula (27). a phenyl substituent; R ¹⁹ represents a monovalent organic group having 1 to 28 carbon atoms, and may also contain an oxygen atom; m' is an integer from 0 to 100, o is an integer from 0 to 100; and c' and d' are 0. Or positive number, e' and f' are 0, a', b', g' and h' are positive numbers; only a'+b'+c'+d'+e'+f'+g'+h'= Further, X' is a divalent organic group represented by the following formula (25) or (26), Y is a divalent organic group represented by the following formula (3), and W is the following formula (4) a divalent organic group represented by the following formula, wherein U is a divalent organic group represented by the following formula (5); Wherein r is an integer of 0 to 10, and R ²⁰ is a hydroxyl group or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms; The dotted line represents a bond, and each of R ⁵ and R ⁶ is an alkyl group or alkoxy group having 1 to 4 carbon atoms, which may be the same or different from each other; and x is any one of 0, 1, and 2; Wherein V is a divalent organic group selected from any one of the following: [Chemical 20] The dotted line represents a bond, p is 0 or 1; each of R ⁷ and R ⁸ is an alkyl group or alkoxy group having 1 to 4 carbon atoms, which may be the same or different; y is any of 0, 1, and 2 By; Wherein the dotted line represents a bond, and T represents an alkylene group having 1 to 10 carbon atoms or a divalent aromatic group having 6 or 10 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group; Wherein the dotted line represents a bond, T and R ^{9 are the} same as defined above, and R ¹⁰ represents a monovalent carboxyl group-containing organic group represented by the following formula (6); In the formula, the dotted line represents a bond, and R ¹¹ to R ¹⁴ are each a different or the same substituent, and represent a hydrogen atom, a halogen atom, a linear one having a carbon number of 1 to 12, a branched, a cyclic alkyl group, and a carbon. The aromatic group of 6 or 10, R ¹¹ and R ¹² , R ¹³ and R ¹⁴ may each be bonded to form a substituted or unsubstituted cyclic structure having 3 to 12 carbon atoms; j is any of 1 to 7 One. The polymer compound containing a polyfluorene skeleton according to Item 8 of the patent application, wherein o in the formula (24) is an integer of 1 to 100, and R ²¹ to R ²⁴ may be the same or different and have a carbon number of 1. a monovalent hydrocarbon group of ~8, R ¹⁸ is a phenyl substituent having a hydroxyl group or an alkoxy group represented by the following formula (27); and R ¹⁹ and R ²¹ to R ²⁴ may be the same or different, and may also contain oxygen. a monovalent organic group having 1 to 10 carbon atoms of the atom, or a phenyl substituent having a hydroxyl group or an alkoxy group represented by the following formula (27) which may be the same as or different from R ¹⁸ ; In the formula, r is an integer of 0 to 10, and R ²⁰ is a hydroxyl group or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. The polymer compound containing a polyoxymethylene skeleton according to the ninth aspect of the invention, wherein the phenyl substituent represented by the formula (27) is one or more selected from the group consisting of the following formula (28). Group; [Chemistry 24] In the formula, the straight line accompanying the wavy line represents the bonding hand. A chemically amplified negative-type photoresist material comprising the following components: (A) a polymer compound containing a polyfluorene skeleton according to any one of claims 1 to 3 and 8 to 10; B) a photoacid generator which decomposes due to light having a wavelength of 190 to 500 nm and generates an acid; (C) a crosslinking agent which is selected from one or more of the following compounds: modified by formaldehyde or formaldehyde-alcohol The obtained amino-based condensate, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and a compound obtained by substituting a hydrogen atom of a hydroxyl group of a polyhydric phenol to an epoxy group, And a compound obtained by substituting a hydrogen atom of a hydroxyl group of a polyhydric phenol to a substituent represented by the following formula (C-1), and a nitrogen atom having two or more epoxy groups having a glycidyl group represented by the following formula (C-2) Compound In the formula, a broken line represents a bond, Rc represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, z represents 1 or 2; (D) a solvent, and (E) a basic compound. A photocurable dry film having a structure in which a photocurable resin layer having a thickness of 10 to 100 μm is sandwiched between a support film and a protective film, wherein the photocurable resin layer is as in claim 11 A chemically amplified negative photoresist material is formed. A method for producing a photocurable dry film, comprising the steps of: (I) continuously applying a chemically amplified negative-type photoresist material according to claim 11 of the patent application to a support film and forming a photocurable resin layer; (II) continuously drying the photocurable resin layer; (III) Further, a protective film is bonded to the photocurable resin layer. A pattern forming method comprising the steps of: (1) applying a chemically amplified negative-type photoresist material as in claim 11 of the patent application to a substrate and forming a photosensitive material film; (2) secondly, heating After the treatment, the photosensitive film is exposed by a high-energy ray or an electron beam having a wavelength of 190 to 500 nm through the reticle; (3) the developing solution is used for development after the heat treatment. A pattern forming method comprising the steps of: (i) adhering a photocurable resin layer exposed by peeling the protective film from the photocurable dry film of claim 12; (ii) exposing the photocurable resin layer to a high-energy ray or an electron beam having a wavelength of 190 to 500 nm in a state in which the support film or the support film is peeled off; (iii) after exposure Heating treatment; and (iv) developing with a developing solution. The pattern forming method according to claim 14 or 15, comprising the step of post-hardening the film patterned by the development at a temperature of 100 to 250 ° C after the developing step. The pattern forming method according to claim 15, wherein the substrate has a substrate having one or both of a groove having a width of 10 to 100 μm and a depth of 10 to 120 μm and a hole. A laminate comprising a substrate laminate having either or both of a groove and a hole having an opening width of 10 to 100 μm and a depth of 10 to 120 μm as claimed in claim 12 It is made of a photocurable resin layer of a dry film. A substrate which is protected by a film obtained by hardening a pattern formed by the pattern forming method according to any one of claims 14 to 17 of the patent application.