WO2005114331A1 - Resist compound and resist composition - Google Patents

Abstract

A resist composition which comprises one or more resist compounds (A) satisfying all of the requirements of (a) having, in the molecule thereof, at least one crosslinking group undergoing a crosslinking reaction directly or indirectly by the irradiation with any radiation selected from the group consisting of a visible light, an ultraviolet ray, an excimer laser, an extreme ultraviolet ray (EUV), an electron beam, an X-ray and an ion beam, (b) having, in the molecule thereof, one or more functional groups selected from the group consisting of a urea group, a urethane group, an amino group and an imido group, (c) having a molecular weight of 500 to 5000, and (d) having a branched structure; and the resist compound. The above resist composition allows the formation of a resist pattern exhibiting an enhanced resolution, which results in the manufacture of a semiconductor element having a higher integration degree.

Description

 Specification

 Resist compound and resist composition

 Technical field

 The present invention relates to a radiation-sensitive resist composition containing a resist conjugate represented by a specific chemical structural formula, which is useful as a non-polymer resist material, and a resist conjugate used therefor. As a radiation-sensitive material that responds to radiation such as ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, and X-rays, it is used in masks for LSI and VLSI production in the electronics field, and has a high-resolution resist pattern. The present invention relates to a resist composition and a resist compound that can be used to manufacture a semiconductor device.

 Background art

 [0002] Conventional resist materials have been polymer materials capable of forming an amorphous thin film. For example, resist, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, X-rays, etc. are applied to a resist thin film produced by applying polymethyl methacrylate and a solvent that dissolves it on a substrate. By irradiation, a line pattern of about 0.1 m is formed.

 However, since the molecular weight distribution of polymer resists is as large as 10,000 to 100,000, the molecular weight distribution is wide.Therefore, in lithography using polymer resists, roughness occurs on the pattern surface in microfabrication and the pattern dimensions are reduced. It becomes difficult to control, and the yield decreases. Therefore, there is a limit to miniaturization in lithography using a conventional polymer-based resist material. In order to produce a finer pattern, various methods for reducing the molecular weight of a resist material have been disclosed.

[0003] Examples of non-polymeric resist materials include (1) positive and negative resists induced by fullerene force, (2) positive and negative resists induced by calixarene force, and (3) starburst resist. Positive resist derived from compound, (4) Posi resist which also induces dendrimer marker, (5) Positive resist which induces dendrimer Z calixarene force, (6) Starburst compound with high branching degree Force induced positive resist and (7) trimming Positive resist derived from a starburst-type compound having an ester bond with an acid as a central skeleton; (8) a negative resist capable of inducing cyclic polyphenolic conjugate; and (9) a polyphenolic conjugate. Induced negative resist, and (10) Calixresorcinarane force induced negative resist.

[0004] Regarding (1), the etching resistance is good, but the applicability and sensitivity have not reached practical levels (see Patent Documents 1 to 5). Regarding (2), a satisfactory pattern cannot be obtained because of poor solubility in a developing solution, which has excellent etching resistance (see Patent Documents 6 to 8). Regarding (3), images may be distorted during heat treatment after exposure due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated, and the heat resistance is low, so that the image may be distorted during the heat treatment after exposure, which is not practical. . The method (5) is not practical because the production process is complicated and the raw materials are expensive (see Patent Documents 12 and 13). Regarding (6), the production process is complicated and the raw materials are expensive, so it is not practical. Regarding (7), the heat resistance is low, so that the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so that it cannot be said that it is practical. See page 14). Regarding (8) and (9), the amorphous property and etching resistance are not sufficient, and improvement is desired (see Patent Documents 15 to 17). With respect to (10), it is desired to improve the amorphous property and the solubility in a safe solvent without being sufficient (see Patent Documents 18 to 19).

 [0005] Patent Document 1 JP-A-7-134413

 Patent Document 2 JP-A-9 211862

 Patent Document 3 JP-A-10-282649

 Patent Document 4 JP-A-11-143074

 Patent Document 5 JP-A-11-258796

 Patent Document 6 JP-A-11-72916

 Patent Document 7 JP-A-11-322656

 Patent Document 8 JP-A-9-236919

 Patent Document 9 JP 2000-305270 A

Patent Document 10: Japanese Patent Application Laid-Open No. 2002-99088 Patent Document 11: JP-A-2002-99089

 Patent Document 12: JP-A-2002-49152

 Patent Document 13: JP 2003-183227 A

 Patent Document 14: Japanese Patent Application Laid-Open No. 2002-328466

 Patent Document 15: JP-A-11-153863

 Patent Document 16: Japanese Patent Application Laid-Open No. 2003-207893

 Patent Document 17: Japanese Patent Application Laid-Open No. 2004-334106

 Patent document 18: JP-A-9-236919

 Patent Document 19: JP 2004-18421A

 Non-Patent Document 1: Proceedings of SPIE vol.3999 (2000) P1202-1206 Disclosure of Invention

 Problems to be solved by the invention

[0006] An object of the present invention is not only to ultraviolet rays such as i-rays and g-rays but also to radiations such as visible light, excimer laser light such as KrF, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam. An object of the present invention is to provide a radiation-sensitive resist composition that can be used and a resist conjugate used for the composition. Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having a high resolution, a high heat resistance and a solvent solubility in a simple manufacturing process, and a resist conjugate used therefor.

 Means for solving the problem

[0007] The present inventors have conducted extensive studies and found that a composition containing a compound satisfying specific conditions is useful for solving the above-mentioned problems.

 That is, the present invention provides a resist composition containing one or more resist compounds (A) satisfying all the conditions (a) to (d).

 (a) Visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam power. It has at least one crosslinkable reactive group in the molecule.

(b) The molecule has at least one functional group selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group. (c) Molecular weight force: 00-5000.

 (d) It has a branched structure.

 The present invention also provides a resistive conjugate suitable for the resistive conjugate (A).

 The invention's effect

 [0008] The use of the resist-bonded product and the resist composition of the present invention makes it possible to produce a high-resolution resist pattern, and to produce a highly integrated semiconductor device. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

 The resist composition of the present invention contains the resist conjugate (A). The resist conjugate (A) in the present invention satisfies all of the following conditions (a) to (d) at the same time.

 (a) Visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam power. It has at least one crosslinkable reactive group in the molecule.

 The resist compound can be selectively solvent-insoluble in the exposed portion by the crosslinking reactive group, and is used for a negative resist composition. Here, the cross-linking reaction means a chemical reaction in which a plurality of reaction points in a resist compound are connected by a covalent bond. The number of the cross-linking reactive groups in the molecule is at least 1, preferably 2, more preferably 2 to 15, particularly preferably 3 to 15. With such a range, the resolution and the image performance can be further improved.

[0010] Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenol group, and a halogenated methyl group. Among these, a carbon-carbon multiple bond group, an epoxy group, a methyl halide group and the like are preferable. Examples of the carbon-carbon multiple bond group include a butyl group (CH = CH 2) and an aryl group.

 2

(CH = CH-CH-), vinylene group-containing group (R ⁴ — CH = CH), acryloyl group (CH

twenty two

 = CH—CO), methacryloyl group (CH = C (CH) —CO), crotonoyl group (CH

2 2 3 3

-CH = CH—CO), humaloneole group (trans type R ⁴ —OC— CH = CH—CO), male

2

A carbon-carbon double bond such as an inyl group (cis-type R ⁴ — OC— CH = CH—CO) Examples include a carbon-carbon triple bond such as a pargyl group (CH≡C) and an acetylene group (R ⁴ —C≡C). Of these, a carbon-carbon double bond such as a buryl group, an aryl group, a vinylene group, an atariloyl group, and a metharylyl group, and a carbon-carbon triple bond such as a propargyl group and an acetylene group are more preferable. Atariloyl, methacryloyl, and propargyl groups are most preferred. Examples of the epoxy group include a glycidyl group (CH (-O-) CHCH-). Examples of the halogenated methyl group include, for example,

twenty two

Methyl group (C1CH-), bromomethyl group (BrCH-) and methyl iodide group (ICH-).

 2 2 2

R ⁴ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

(b) The molecule has at least one functional group selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.

The resist conjugate (A) has at least one functional group selected from the group consisting of a urea group, an amide group, a urethane group, and an imide group, in particular, a group consisting of a urea group, an amide group, and a urethane group. It is preferable that one or more and at least three functional groups are selected. Further, it may contain a functional group having another nitrogen component. Other functional groups include a tertiary amine group; a quaternary ammonium group; an imino group; an azide group; a function containing a heterocyclic amine such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, and morpholine. But not limited to. By having the above-mentioned functional group, it is possible to have heat resistance and substrate adhesion necessary for pattern production, and further improve resolution. Further, the process for producing a compound having a molecular weight of about 500 to 5,000 can be simplified. In addition, it is preferable not to include a basic functional group. If the compound has a basic functional group, the sensitivity may be reduced. Each of the branched molecular chains in the branched structure has at least one cross-linking reactive group, and each of the molecular chains has an urea bond, a urethane bond, an amide bond, and an imide bond (preferably, , A rare bond, and a urethane bond). With the above structure, the substrate adhesion can be improved, and the resolution can be further improved. (C) The molecular weight is from 500 to 5,000.

 The molecular weight is 500-5000, preferably <600-3000, more preferably <700-2000. When the content is in the above range, good film-forming properties can be imparted, and the resolution and alkali developing performance can be further improved.

(D) It has a branched structure.

 In the present invention, the “branched structure” refers to a structure that satisfies at least one of the following (1) to (4).

 (1) It has a tertiary carbon atom or tertiary nitrogen atom not included in the cyclic structure.

 (2) It has a quaternary carbon atom.

 (3) It contains at least one aromatic or aliphatic ring having three or more substituents.

 (4) It has a tertiary phosphorus atom.

 (5) It contains at least one isocyanurate ring.

 By having the above-mentioned branched structure, a stable amorphous property can be imparted over a long period of time, and the resist material has excellent film forming properties, light transmittance, solvent solubility, etching resistance, etc. necessary for pattern formation. Has features. Further, since the number of photosensitive groups can be increased, sensitivity can be increased.

 In the present invention, it is preferable that the resist conjugate (A) satisfies F ≦ 5 (F represents the total number of atoms Z (the total number of carbon atoms and the total number of oxygen atoms)). When F is 5 or less, performance such as resolution and etching resistance does not deteriorate.

 [0015] The resistive conjugate (A) in the present invention is preferably represented by the following formula (1).

 [Chemical 1]

[式（1)中、 Xは下記式 (I) :

[In the formula (1), X is the following formula (I):

[Formula 2]

で表され、式（1)中少なくとも 3以上有し；

Having at least 3 or more in formula (1);

 E is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;

 s, t, and u each independently represent an integer of 0 to 3, and a plurality of E, X, Z, and Y may be the same or different.

(In the above formula (I), R ¹ is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms. To 12 one-branched alkyl radicals, which are selected substituents;

 Α is a hydrogen atom or a substituent selected from the group consisting of an aryloxy group, an atariloyloxy group, a glycidyloxy group and a chloromethyloxy group, and at least one of A is an aryloxy group, Atalyloyloxy, glycidyloxy, and chloromethyloxy groups which are selected substituents;

 Ar is an aromatic hydrocarbon group having 6 to 12 carbon atoms;

 Y is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, a substituted alkylene group having 1 to 12 carbon atoms, or a single bond;

 Z represents a single bond or a substituent selected from the group consisting of O, —S, and —NH;

 al is an integer from 1 to 9;

 rl is an integer from 0 to 8;

 al + rl≤9

A、 Ar、 al、 rlは、各々同一でも異なっていても よい。）] n is 1. However,

A, Ar, al, rl may be the same or different Good. )]

 In the formulas (1) and (I),

 Examples of the linear hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Hexyl, octyl, decyl, dodecyl and the like;

 Examples of the cyclic hydrocarbon group having 3 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclododecyl and the like;

 Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Xyloxy, octyloxy, dodecyloxy, and the like;

 Examples of the one-branched alkyl group having 3 to 12 carbon atoms include isopropyl, sec-butyl, t-butyl, 1,1-dimethylpropyl, 1-methylbutyl, 1,1-dimethylbutyl, and 1-methyl And a didecane group;

 Examples of the divalent acyclic hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a dimethylmethylene group, a trimethylene group, a tetramethylene group, a t-butylene group, a hexylene group, an otathylene group, Dodecylene groups and the like;

 Examples of the divalent cyclic hydrocarbon group having 3 to 12 carbon atoms include a phenylene group, a tolylene group, a naphthylene group, a cyclopentylene group, a cyclohexylene group, and a cyclododecylene group;

 Examples of the substituted alkylene group having 1 to 12 carbon atoms include an aminomethylene group, a hydroxylmethylene group, a carboxylmethylene group, a chloromethylene group, a bromomethylene group, an odomethylene group, a methoxymethylene group, an ethoxymethylene group, a propoxymethylene group, Butoxymethylene group, acetylmethylene group, cyanomethylene group, nitromethylene group, etc .; Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, and naphthyl group. And a biphenyl group.

[0018] The compound of the formula (1) is an isocyanurate derived from diisocyanate, After the reaction of phenols or hydroxyalkylphenols, a crosslinking reaction occurs by irradiation with visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, or ion beam, or a chemical reaction induced by the irradiation. Cross-linking reactive group introduction It is manufactured by reacting a reagent. By using isocyanurate derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.

[0019] The method for producing the resist conjugate (A) used in the present invention is not particularly limited. In particular, polyisocyanates having three or more isocyanate groups, aminophenols or hydroxyalkylphenols are used. After the reaction, a crosslinking reactive group-introducing reagent that causes a crosslinking reaction by irradiation with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, or ion beam, or a chemical reaction induced by the irradiation is used as a base. The production method of reacting in the presence of a catalyst is preferred because all the steps can be produced in the same reaction vessel, which is simpler and more practical.

 [0020] The isocyanurate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene diisocyanate, cyclohexanediisocyanate. , Isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanatemethyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine Preferably, it is either diisocyanate, tetramethylxylene diisocyanate, or isocyanurate derived from trimethylhexamethylene diisocyanate. Among them, isocyanurate derived from tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, bis (isocyanatemethyl) cyclohexane, and meta-xylene diisocyanate Particularly preferred are tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, and isocyanurate derived from bis (isocyanatemethyl) cyclohexane.

The aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a functional group having higher reactivity with isocyanate than phenolic hydroxyl groups. Examples of the aminophenols include p-aminophenol, m-aminophenol, o-aminophenol, 4 aminocatechol, 3 aminocatechol, 2 aminoresorcinol, 4 aminoresorcinol, 5 aminoresorcinol, 2 aminohydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, 2-aminomethylphenol, 3-aminomethylphenol, 4-aminomethylphenol, 4-aminomethylcatechol, 3-aminomethylcatechol, 2-aminomethylresorcinol, 4-aminomethylresorcinol, 5 aminomethylresorcinol, 2aminomethylhydroquinone, 4-aminomethylpyrogallol, 5aminomethylpyrogallol, 2aminophloroglicinol, 2aminomethylphloroglicinol and the like. The Particularly, p-aminophenol and _m- aminophenol are preferred.

 [0022] Examples of the hydroxyalkylphenols include 4-hydroxymethylphenol, 3-hydroxymethylphenol, 2-hydroxymethylphenol, 4-hydroxymethylcatechol, 3-hydroxymethylcatechol, 2-hydroxymethylresorcinol, and 4-hydroxymethylresorcinol. , 5-hydroxymethylresorcinol, 2-hydroxymethylhydroquinone, 4-hydroxymethylpyrogallol, 5-hydroxymethylpyrogallol and the like. In particular, 4-hydroxymethylphenol and 5-hydroxymethylresorcinol are preferred!

The reaction of the isocyanurate with an aminophenol or a hydroxyalkylphenol and a crosslinking reactive group-introducing agent is carried out by dissolving an aminophenol or a hydroxyalkylphenol in an aprotic polar solvent, and then dissolving the aminophenol or the hydroxyalkylphenol in the aprotic polar solvent. Adding isocyanurate dissolved in a protic polar solvent; adding isaminophenol or hydroxyalkyl phenol dissolved in an aprotic polar solvent to isocyanurate dissolved in an aprotic polar solvent; and Stir for about 5 minutes to 24 hours. When the compound having three or more isocyanate groups is a liquid, it does not have to be dissolved in an aprotic solvent. It is preferable to drop the solution at a temperature of about 5 ° C to 100 ° C over about 1 to 150 minutes. Thereby, it selectively reacts with an amino group or a hydroxyalkyl group isocyanate group. Although the reaction proceeds without a catalyst, the reaction speed may increase when one or more base catalysts are used. Next, in order to introduce a cross-linking reactive group such as an atalyloyl group in the same reaction vessel, a cross-linking reactive group-introducing agent such as an atalyl-based iuclide is introduced in the presence of the above-mentioned base catalyst such as triethylamine. And at room temperature for 2-4 hours. Distilled water is added to the reaction solution to precipitate crystals, which are then washed with distilled water, purified by Z or column chromatography, high-performance liquid chromatography, etc., and dried to obtain the resist-bonded product (A).

[0025] The crosslinking reactive group-introducing agent referred to herein includes an acid, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, an epihalohydrin, etc. having a crosslinking reactive group. , Meta-atalyloinochloride, atariloinochloride, bromoethylene, bromopropene, 1-propininolepheninolechloride, chlorostyrene, bromochloromethane, 1-bromomethyl-4 chloromethylbenzene, and particularly, atariloinochloride, 3 -Bromopropene, epichlorohydrin, epibu mouth mohydrin, bromochloromethane are preferred. The crosslinking reactive group includes a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenol group, a chloromethyl group, and the like.

 As the aprotic polar solvent used in the above reaction, a compound having three or more isocyanate groups, an aminophenol or a hydroxyalkylphenol, a reagent for introducing a cross-linking reactive group, and a product such as resist As long as the substance (A) can be dissolved, a conventionally known aprotic polar solvent, which is not particularly limited, can be used. For example, dimethylformamide, dimethylacetamide and the like can be mentioned. These may be used alone or in combination of two or more.

 [0027] The base catalyst used in the above reaction may be any alkaline conjugate, such as mono, di- or trialkylamines, mono-, di- or trialkanolamines, and heterocyclic compounds. It is preferable to use at least one of an alkali compound such as amines, tetramethylammonium hydroxide (TMAH) and choline, and a metal compound such as an alkylammonium salt and an alcoholate. Among them, trialkylamines such as triethylamine, triisopropylamine, and tributylamine are preferred, and triethylamine is particularly preferred.

[0028] In another method, after the above-mentioned isocyanurate is reacted with an aminophenol or a hydroxyalkylphenol, the reaction solution is added to a large amount of water to crystallize, and the filtered crystal is dissolved in acetone. Then, it is again added to a large amount of water and crystallized, and To obtain a polyphenol conjugate. Then, in the same or another container, in order to introduce a cross-linking reactive group such as an atalyloyl group and a polyphenol conjugate, a cross-linking reactive group-introducing agent such as an atari-mouth ilk mouth-ride is introduced with a reagent such as triethylamine. The reaction is carried out at normal pressure and room temperature for 2 to 4 hours in the presence of the base catalyst. Distilled water is added to the reaction solution to precipitate crystals, which are then washed with distilled water, purified by Z or column chromatography, high-performance liquid chromatography, or the like, and dried to obtain the resisted conjugate (A).

Further, after reacting the above-mentioned isocyanurate with an aminophenol or a hydroxyalkylphenol, the reaction solution is crystallized by adding it to a large amount of water, and the filtered crystals are dissolved in acetone. Then, it is again added to a large amount of water and crystallized to obtain a polyphenol conjugate as an intermediate. Then, in the same or another container, a crosslinking reactive group-introducing agent such as 3-bromopropene is introduced with potassium carbonate and iodide in order to introduce a crosslinking reactive group such as an aryl group and the like. The reaction is carried out at normal pressure and room temperature for 2 to 40 hours in the presence of a catalyst such as sodium. After removing the salt from the reaction solution and concentrating the solvent, the residue is washed with distilled water, purified by Z or column chromatography, high performance liquid chromatography or the like, and dried to obtain the resist-bonded product (A).

 [0030] Among the compounds represented by the formula (1), those further represented by the following formulas (4) to (6) are preferable.

[Formula 3]

式 (4)〜（6)中、 Xと Eは前記と同様である。

In the formulas (4) to (6), X and E are the same as described above.

The compounds of the formulas (4) to (6) are reacted with isocyanurate derived from diisocyanate and an aminophenol or hydroxyalkylphenol, and then reacted with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV ), Electron beam, X-ray and ion beam irradiation, or a chemical reaction induced by the irradiation, or a cross-linking reactive group-introducing reagent which causes a cross-linking reaction. By using isocyanurate derived from diisocyanate, a branched polyphenol conjugate having a branched structure can be easily obtained.

 As the isocyanurate derived from diisocyanate, the above compounds can be used.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

[0032] The reaction of an isocyanurate derived from diisocyanate with an aminophenol or a hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group is carried out by reacting the above compound having three or more isocyanate groups with an aminophenol or Hydroxyalkylpheno The reaction can be carried out in the same manner as in the reaction with the reactive group and the reagent for introducing a crosslinking reactive group. After completion of the reaction, the compounds of formulas (4) to (6) of the corresponding monomers can be selectively obtained by separation by column chromatography or by using monomeric isocyanurate as a raw material. It comes out.

 Among the compounds represented by the formulas (4) to (6), particularly preferred are compounds represented by the following formulas (191) to (23-4).

[Formula 4]

f/X3d 91- TCCMl/SOOZ OAV

f / X3d 91- TCCMl / SOOZ OAV

[9 ^]

l7Z600/S00Zdf/X3d 91·

l7Z600 / S00Zdf / X3d 91

[Formula 7]

() 2031

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

 The resist conjugate (A) in the present invention is more preferably one represented by the following formula (2).

[Formula 14] GH-x (2)

[In the formula (2), X is the same as described above, and a plurality of Xs may be the same or different.

 [Formula 15]

のいずれかの構造から誘導される特性基であり、 Xは式 (i)〜(v)中の芳香環または 脂肪族環に 3以上結合して 、る。 Vは 3〜 15の整数を表す。

Wherein X is bonded to an aromatic ring or an aliphatic ring in formulas (i) to (v) three or more times. V represents an integer of 3 to 15.

(In the above formulas (i) to (ii), R is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon R ³ is a hydrogen atom, a hydroxyl group, a non-cyclic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic carbon group having 3 to 12 carbon atoms. A hydrogen group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi):

[Formula 16]

(In the formula (vi), E ² is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, and a divalent hydrocarbon group having 3 to 12 carbon atoms. Or a substituted alkylene group having 1 to 12 carbon atoms. ) Is also a group strength which is also a selected group, r is an integer of 0 to 4 and k is an integer of 1 to 7. However, a plurality of r may be the same or different.

 In the formulas (iv) to (v), E ′ may be the same or different and each independently represents a single bond, a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, 3 to 12 carbon atoms. And a substituted alkylene group having 1 to 12 carbon atoms, wherein X in the formula (2) is bonded to E ′. }]

[0038] A linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a 1-branch having 3 to 12 carbon atoms of the formula (2) The alkyl group, the divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, the divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, and the substituted alkylene group having 1 to 12 carbon atoms are the same as those in the formula (1). Can be exemplified.

 Examples of the substituted alkyl group having 1 to 12 carbon atoms include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a chloromethyl group, and a bromomethyl group. Nitromethyl group, methoxyethyl group, methylthioethyl group, ethoxyxethyl group, ethylthioethyl group, methoxyethoxyxyl group, benzyloxyethyl group, benzylthioethyl group, chloroethyl group, bromoethyl group, nitroethyl group, etc. be able to.

 The compound of the formula (2) is produced by reacting an oligomer of monoisocyanate or triisocyanate with an aminophenol or a hydroxyalkylphenol. By using a monoisocyanate oligomer or triisocyanate, a branched polyphenol conjugate can be easily obtained.

[0040] The oligomer of monoisocyanate or triisocyanate is not particularly limited, but oligomers of isocyanate methane, tris (isocyanate phenyl) methane, tris (isocyanate phenyl) thiophosphate, mesitylene trimethane Isocyanate, triisocyanate benzene, lysine ester triisocyanate, 1,6,11- decanetriisocyanate, 1,8 diisocyanate 4 isocyanate methyloctane, 1,3,6 hexamethylene tri It is preferred that the isocyanate or the bicycloheptane triisocyanate be selected. Among them, oligomers of isocyanate methane, tris (isocyanate phenol) methane, and tris (isocyanate phenyl) thiophosphate are particularly preferred. preferable.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 [0041] The reaction of the oligomer of monoisocyanate or triisocyanate with the aminophenols or hydroxyalkylphenols and the reagent for introducing a cross-linking reactive group is carried out by the above-mentioned isocyanurate derived from diisocyanate, and aminophenol. The reaction can be carried out in the same manner as in the reaction with a compound or a hydroxyalkylphenol and a crosslinking reactive group introduction reagent.

 [0042] Among the compounds represented by the formula (2), those represented by the following formulas (9) to (14) are preferable.

 [Formula 17]

[Formula 18]

In the formulas (9) to (14), X, R ² and k are the same as described above.

 Compounds of the formula (9) include tris (isocyanate phenyl) methane and amino phenols.

, A hydroxyalkylphenol and a crosslinking reactive group-introducing agent. By using tris (isocyanatephenyl) methane, a branched polyphenol conjugate can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 The reaction between tris (isocyanate phenol) methane and an amino phenol or a hydroxyalkyl phenol is carried out by the above-mentioned isocyanurate derived from diisocyanate, an amino phenol or a hydroxyalkyl phenol and a crosslinking reactive group. The reaction can be carried out in the same manner as in the reaction with the introduced reagent.

[0044] The compound of the formula (10) includes tris (isocyanate phenyl) thiophosphate, It is produced by reacting phenols or hydroxyalkylphenols. By using tris (isocyanatephenyl) thiophosphate, a branched polyphenol compound can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 The reaction between tris (isocyanatephenol) thiophosphate and an aminophenol or a hydroxyalkylphenol is carried out by reacting the above-mentioned isocyanurate derived from diisocyanate with an aminophenol or a hydroxyalkylphenol. This can be done in a similar way.

 [0045] The compound of the formula (11) is produced by reacting an oligomer of isocyanate phenol, an aminophenol or a hydroxyalkylphenol, and a reagent for introducing a crosslinking reactive group. By using an oligomer of isocyanate phenol, a branched polyphenol conjugate can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 The reaction between an oligomer of isocyanate phenol and an aminophenol or a hydroxyalkylphenol is carried out by reacting the isocyanurate derived from the diisocyanate with an aminophenol or a hydroxyalkylphenol and crosslinking reactivity. The reaction can be performed in the same manner as in the reaction with the group introduction reagent.

 The compound of the formula (12) is produced by reacting mesitylene triisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group-introducing agent. By using mesitylene triisocyanate, a branched polyphenol compound can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

The reaction between mesitylene triisocyanate and an aminophenol or a hydroxyalkylphenol is carried out in the same manner as the reaction between the isocyanurate derived from diisocyanate and the aminophenol or a hydroxyalkylphenol. With Wear.

 [0047] The compound of the formula (13) is produced by reacting triisocyanate benzene, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. By using triisocyanate benzene, a branched polyphenol conjugate can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 The reaction of triisocyanate benzene with an aminophenol or hydroxyalkylphenol is carried out by reacting the isocyanurate derived from diisocyanate with an aminophenol or hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group. This can be performed in the same manner as described above.

[0048] The compound of the formula (14) is produced by reacting cyclohexanetriisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. By using cyclohexanetriisocyanate, a branched polyphenol conjugate can be easily obtained.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 The reaction of cyclohexanetriisocyanate with an aminophenol or a hydroxyalkylphenol is carried out by reacting the isocyanurate derived from the diisocyanate with an aminophenol or a hydroxyalkylphenol and a reagent for introducing a crosslinking reactive group. Can be carried out in the same manner as in the above reaction.

[0049] Among the compounds represented by the formulas (9) to (14), particularly preferred are compounds represented by the following formulas (26-1) to (32-4).

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[化 27]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

n

i7r60o/soozdf/x3d ΐεε ΐ/sooz OAV

i7r60o / soozdf / x3d ΐεε ΐ / sooz OAV

[Formula 32]

[式 (3)中、 R³は水素原子、炭素数 1〜12の非環状炭化水素基、炭素数 3〜12の環 状炭化水素基、および炭素数 1〜12の置換アルキル基力もなる群力も選ばれる置換 基であり、 X、 E²および kは前記と同様であり、

[In the formula (3), R ³ is a group comprising a hydrogen atom, an acyclic hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkyl group having 1 to 12 carbon atoms. X, E ² and k are the same as described above;

 B is the formula (vi):

[0051]

(In the formula (vi), X and E ² are the same as described above.)

E¹'、 E²、 Jは、各々同 一でも異なっていてもよい。 ] And E ¹ and E ¹ ′ may be the same or different and each independently represents a single bond or a divalent hydrocarbon group having 1 to 11 carbon atoms. However, the total number of carbon atoms of E ¹ and E ¹ is 0 to: L 1. J is a substituent selected from —O—, —S—, —NH— and a single bond. However, multiple B,

E ¹ ′, E ² , and J may be the same or different. ]

The non-cyclic hydrocarbon group, a cyclic hydrocarbon group having 3 to 12 carbon atoms, and substituted alkyl group having 1 to 12 carbon atoms having 1 to 12 carbon atoms represented by R ³ of [0052] Formula (3), the formula ( The same as 1) can be exemplified.

In the formulas (3) and (vi), a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkylene group having 1 to 12 carbon atoms are represented by the formula: The same as (1) can be exemplified. Examples of the divalent hydrocarbon group having 1 to 11 carbon atoms ¹ , E ¹ ′) include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, pendecylene, and the like.

[0053] The compound of the formula (3) is produced by reacting a burette derivative, an allohanate derivative, or a urethane derivative derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. Is done. By using a burette, an allohanate or a urethane derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained. [0054] The burette form, allohanate form, or urethane form derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanatecyclohexyl) Methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanatemethyl) cyclohexane, meta-xylene diisocyanate, Any burette, allohanate, or urethane derivative derived from norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or trimethylhexamethylene diisocyanate. In the preferred to be either. Among them, a buret derivative derived from hexamethylene diisocyanate and a urethane derivative derived from tolylene diisocyanate are particularly preferred.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 [0055] The reaction of a burette, allohanate, or urethane derivative derived from diisocyanate with an aminophenol or hydroxyalkylphenol is carried out by reacting the above-described isocyanurate derived from diisocyanate with an aminophenol or hydroxyalkanol. The reaction can be carried out in the same manner as in the reaction with a kilnphenol and a reagent for introducing a crosslinking reactive group.

 [0056] Among the compounds represented by the formula (3), those represented by the formula (8) are preferable.

 [Formula 35]

式 (8)中、

X、 J、 kは前記と同様である。但し、複数個の 、 E²、 X、 Jは、各 々同一でも異なっていても良い。

In equation (8),

X, J and k are the same as above. However, a plurality of, E ² , X, J Each may be the same or different.

 The compound of the formula (8) is produced by reacting a urethane compound derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. By using a urethane derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.

 [0058] The urethane form derived from diisocyanate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene diisocyanate, cyclohexane. Hexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate , Naphthalenediisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or a urethane derivative derived from trimethylhexamethylene diisocyanate. Among them, urethane derivatives derived from tolylene diisocyanate are particularly preferred.

 The above-mentioned compounds can be used as the aminophenol or the hydroxyalkylphenol.

 [0059] The reaction between the urethane compound derived from diisocynate and the aminophenol or hydroxyalkylphenol is carried out by the above-described isocyanurate derived from diisocyanate, the aminophenol or hydroxyalkylphenol, and the crosslinking. The reaction can be carried out in the same manner as in the reaction with the reactive group introduction reagent.

 Among the compounds represented by the formula (8), particularly preferred are compounds represented by the following formulas (24-1) to (24-4).

[Formula 36]

式（7)中、 E²、 Xおよび kは前記と同様である。 [Formula 37]

In the formula (7), E ² , X and k are the same as described above.

 [0062] The compound of the formula (7) is produced by reacting a burette derivative derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a reagent for introducing a crosslinking reactive group. By using a burette derivative derived from diisocyanate, a branched polyphenol conjugate can be easily obtained.

 [0063] The burette form derived from diisocyanate is not particularly limited, but is tolylene diisocyanate, bis (isocyanate phenyl) methane, bis (isocyanate cyclohexyl) methane, phenylene isocyanate, cyclo Hexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate Preferably, it is any one of a burette derivative derived from a salt, naphthalene diisocyanate, lysine diisocyanate, tetramethyl xylene diisocyanate, or trimethylhexamethylene diisocyanate. Of these, a burette derivative derived from hexamethylene diisocyanate is particularly preferred.

 As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.

 [0064] The reaction between the burette derivative derived from diisocyanate and the aminophenols or hydroxyalkylphenols is carried out by reacting the isocyanurate derived from diisocyanate with the aminophenols or hydroxyalkylphenols and the crosslinking reactive group. The reaction can be performed in the same manner as in the reaction with the introduced reagent.

 Particularly preferred among the compounds represented by the formula (7) are compounds represented by the following formulas (25-1) to (25-4).

[Formula 39]

[Formula 40]

本発明におけるレジストイ匕合物 (A)は、前記式（1)〜（14)中の Xが下記式 (11)〜（ III)で表されるものが好ましい。

The resist conjugate (A) in the present invention is preferably one wherein X in the above formulas (1) to (14) is represented by the following formulas (11) to (III).

[Formula 41]

 (II) (III) In the formulas (II) to (III), A is the same as described above, and m is an integer of 1 to 2.

The compound in which X is represented by the formula (II) is produced by reacting a compound having three or more isocyanate groups, an aminophenol and a reagent for introducing a crosslinking reactive group. The compound in which X is represented by the formula (III) is produced by reacting a compound having three or more isocyanate groups with a hydroxyalkylphenol. By using a compound having three or more isocyanate groups, a branched polyphenol conjugate having a branched structure can be easily obtained.

 As the compound having three or more isocyanate groups, the above compounds can be used.

 Aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a higher reactivity with isocyanate than the phenolic hydroxyl group and have a functional group.

[0068] Examples of the aminophenols used for producing the compound represented by the formula (II) wherein X is, for example, P-aminophenol, m-aminophenol, o-aminophenol, 4-aminocatechol, ₃ -aminocatechol , 2 aminoresorcinol, 4 aminoresorcinol,

Examples thereof include 5-aminoresorcinol, 2-aminohydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, and 2-aminophloroglicinol. Particularly, p-aminophenol and m-aminophenol are preferred.

[0069] Examples of the hydroxyalkylphenols used for producing the compound represented by the formula (III) wherein X is 4 hydroxymethylphenol, 3 hydroxymethylphenol, 2 hydroxymethylphenol, 4-hydroxymethylphenol, Examples include methyl catechol, 3-hydroxymethyl cate hydroxymethyl resorcinol, 2-hydroxymethyl hydroquinone, 4-hydroxymethyl virogallol, 5-hydroxymethyl virogallol, and the like. Especially 4 Hydroxymethylphenol and 5-hydroxymethylresorcinol are preferred. The reaction of a compound having three or more isocyanate groups with an aminophenol or a hydroxyalkylphenol can be carried out by the method described above.

 [0070] The nitrogen content of the resist conjugate (A) is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 5 to 15% by mass. Is particularly preferred. When the content of the nitrogen element is in the above range, the sensitivity and the resolution are excellent, and the heat resistance and the substrate adhesion required for pattern formation can be obtained.

 Further, the resist compound (A) is a compound obtained by reacting hydroxybenzoic acid, dihydroxybenzoic acid, or trihydroxybenzoic acid with a crosslinking reactive group-introducing agent under a base catalyst, and an amino group Can also be obtained by condensing a compound having three or more of This method is preferable because by-products can be suppressed.

 [0072] The compound having three or more amino groups is not particularly limited, but includes mesitylenetriamine, triaminobenzene, pararoselin, tris (aminophenol-methane), tris (aminophenyl) thiophosphate. , Lysine ester triamine, 1,6,11-pandecanthramine, 1,8-diamino-14-aminomethyloctane, 1,3,6-hexamethylenetriamine, bicycloheptanetriamine, norbornanetriamine, etc. No. Among these compounds, mesitylenetriamine, triaminobenzene and pararoselin are particularly preferred.

 The resist compound (A) is obtained by reacting a compound obtained by reacting an aminophenol or a hydroxyalkylphenol with a crosslinking reactive group-introducing agent in the presence of a base catalyst, and a carboxyl group. It can also be obtained by condensing a compound having 3 or more. This method is preferable because by-products can be suppressed.

 Examples of the compound having three or more carboxyl groups include benzenetetracarboxylic acid, cyclohexanetetracarboxylic acid, benzenetricarboxylic acid, and cyclohexanetricarboxylic acid, and particularly, benzenetricarboxylic acid such as trimesic acid and each hydrogenated trimesic acid. And cyclohexanetricarboxylic acid are preferred.

[0074] The resist composition of the present invention contains one or more resist compounds (A) described above. When one kind of the resistive conjugate (A) is used, a high resolution can be obtained, and when two or more kinds are used, the film formability and the substrate adhesion may be improved. [0075] The resist composition of the present invention can be directly irradiated with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam. Alternatively, it is desirable to add a compound (B) which generates a radical or a cation indirectly.

[0076] Among the compounds (B), as the compound (B-1) that generates a radical, a compound that generates a radical by interacting with a radical initiator or a photo-excited sensitizer, mainly a compound, mainly Compounds having both the sensitizing action by ultraviolet light and the ability to generate radicals due to the action are mentioned. Examples of the radical initiator include peroxides such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, and tamen hydroperoxide; azobisisobutymouth-tolyl, azobiscyclohexane Azo conjugates such as -tolyl and phenyl-trifluoromethane; persulfates such as potassium persulfate and ammonium persulfate; and persulfates such as triethylaluminum, trimethylaluminum, ethylaluminum-dimethyldichloride, and getylaluminum chloride. Organic aluminum compounds; other organic metal compounds such as tetraethyl lead, getyl zinc, getyl cadmium, and tetraethyl tin; titanium tetrachloride, titanium trichloride, aluminum chloride aluminum, aluminum bromide, stannic chloride, salt Zinc oxide, boron trifluoride, boron trifluoride Chloride such as tiletherate and phosphorus pentafluoride are exemplified. Examples of the above-mentioned compounds which generate a radical by interacting with the photoexcited sensitizer in some way include, for example, various titanocenes described in JP-A-59-152396 and JP-A-61-151197. (Specifically, di-cyclopentagel Ti dichloride, dicyclopentagel Ti bis-phenyl, dicyclopentagenyl Ti-bis 2,3,4,5,6 Pentafluorophenyl-1-yl, di-cyclopentagenenyl-bis-1,2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenenyl-Ti-bis-1,2 4,6-trifluorophenyl 1-yl, dicyclopentagenenyl-Ti-2,6 di-fluorophenyl-1-yl, di-cyclopentagenenyl Ti-bis-1,2,4-difluorophenyl 1-yl, di-methylcyclo mouth pentagenenyl-ti-bi 1,2-, 4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentagenenyl-Ti-bis-1,2,6-difluorophenyl-1-yl, di-cyclopentageninole One Ti-bis 2,6 Difno Leoro 3— (Pinole 1-Inore) 1-yl), Bull. Chem. Soc. Japan. 33, 565 (1960) and J. Org. Chem. 36 [16] 2262 (1971). Hexariylbiimidazoles (specifically, 2,2, -bis (o-chlorophenol) -4,4 ', 5,5, -tetra (ρ-fluorophenyl) biimidazole, 2,2 , —Bis (o-bromophenyl) 4,4,5,5,1-tetra (p-phenyl) biimidazole, 2,2,1-bis (o-chlorophenol) 4,4,5,5 , 1-tetra (p-chloro-naphthyl) biimidazole, 2,2,1-bis (o-chloro-or-phenyl) -1,4,4,5,5,1-tetra (p-chloro-or-phenyl) biimidazole, 2,2, -bis (obromophenyl) -1,4,4,5,5,1-tetra (p-methoxyphenyl) biimidazole, 2,2,1-bis (ochlorophenol) Le) 1, 4, 4, 5, 5, 1 tetra (o, p dichloromethane) 1,2,1,2-bis (o-methyl phenol) -1,4,4,5,5,1-tetra (o, p-dibromophenol) biimidazole, 2,2, — Bis (o bromophenyl) —4,4,5,5,1-tetra (o, p-dichlorophenyl) biimidazole, 2,2,1-bis (o, p-dichloromouth phenol) -1,4 Hexaryl biimidazoles having a halogen substituent on the benzene ring, such as 4,5,5,5,1-tetra (o, p-dichlorophenyl) biimidazole, etc.), hydrogenated hydrocarbon derivatives, dia Lilledonium salts, organic peroxides and the like. Examples of the compound having both the sensitizing action mainly by ultraviolet light and the ability to generate radicals thereby include, for example, 2,2-dimethoxy-1,2-diphenyl-l-etane-1-one, 2-isopropoxy-1,1, 2-Diphenyl-1-ethane, (1'-hydroxycyclohexyl) phenyl ketone, 2-methyl-11 (4'-methylthiophene) 2 morpholinopropane 1-, 2-benzyl-2 (N, N dimethylamino)-1- (4'-morpholinophenyl) butan-1-one, 2-hydroxy-12-methyl-1-phenylpropane-11-one, 2,4,6 trimethylbenzoy Fe-ketone derivatives such as ludiphen-l-phosphinoxide, 1- [4 '-(2-hydroxyethoxy) phenyl]-2-hydroxy-12-methyl-1-propane-1-one, 4- (N , N-dimethylamino) isoamyl benzoate, 4— ( N, N Jimechiruamino) benzoic acid esters such as benzoic acid Echiruesuteru, (7 ⁵ -? 2, 4 - cyclopentadiene one 1-I le) [(1, 2, 3, 4, 5, 6 7)? — (1-Isopropylbenzene) Examples thereof include organometallic compounds such as ironhexafluorophosphate, and heteroaromatic compounds such as 2,4-getyl thioxanthone. Among the compounds (B), compounds (B-2) that generate cations are represented by the following formulas (33) to (33)

Compound power represented by 40) At least one selected from the group powers.

[0078] [Formula 42]

In the formula (33), R may be the same or different and each independently represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms. A cyclic alkyl group having 3 to 12 carbon atoms, a linear alkoxy group having 1 to 12 carbon atoms, a branched alkoxy group having 3 to 12 carbon atoms, a cyclic alkoxy group having 3 to 12 carbon atoms, a hydroxyl group, or halogen X— is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a halogen-substituted aryl group having 6 to 12 carbon atoms. A sulfonic acid ion or a halide ion.

[0080] The compound represented by the formula (33) includes triphenylsulfo-dimethyltrifluoromethanesulfonate, triphenylsulfo-dimethylnonafluoro-n-butanesulfonate, triphenylsulfo-dimethyltrifluoromethanesulfonate, triphenylsulfo-dimethyltrifluoromethanesulfonate, octanesulfonate, Diphenyl 4-methylphenyl sulfo-dimethyltrifluoromethanesulfonate, diphenyl 2,4,6 trimethylphenyl sulfo-dimethyltrifluoromethanesulfonate, diphenyl 4-t-butoxyphenyl sulfo-dimethyltrifluoro Fluoromethanesulfonate, diphenyl 4-t-butoxyphenylsulfo-dumnonafluoron butanesulfonate, diphenyl 4-hydroxyphenylsulfo-dimethyltrifluoromethanesulfonate, bis (4-fluorophenol) 4-hydroxyphenylsulfo -Pemtrifluoromethanesulfone , Diphenyl-hydroxyphenylsulfo-dimethylnonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfo-dimethyltrifluoromethanesulfonate, tris (4-methoxyphenyl) sulfo-ゥ Trifluoromethanesulfonate, tris (4-fluorophenyl) sulfur H-dimethyltrifluoromethanesulfonate, triphenylsulfo-dimethyl p-toluenesulfonate, triphenylsulfo-dimethylbenzenesulfonate, diphenyl-ru 2,4,6 trimethylphenyl p-toluenesulfonate, diphenyl-ru 2,4,6 Trimethylphenol sulfo-dimethyl 2 trifluoromethylbenzenesulfonate, diphenyl 2,4,6—Trimethylphenol sulfo-dimethyl4 Trifluoromethylbenzenesulfonate, diphenyl 2,4 , 6 Trimethylphenylsulfo-dimethyl 2,4 difluorobenzenesulfonate, diphenyl 2,4,6 Trimethylphenylsulfo-dimethylhexafluorobenzenesulfonate, diphenylnaphthyl sulfo-II Mutifluoromethanesulfonate, dipheninole 4-Hydroxyphen-norresnorefonep Over bets, bird whistle - Honoré sulfo - © beam 10-camphorsulfonate, and Jifue - Lu 4-hydroxy Hue Nirusuruho - © is preferable that the beam is at least one kind selected from the group consisting of one 10-camphorsulfonate.

 [0081]

式（34)中、 X—および R²⁴は、式（33)の X—および R²³と同様である。

In the formula (34), X— and R ²⁴ are the same as X— and R ^{23 in the} formula (33).

[0082] The compound represented by the formula (34) includes bis (4t-butylphenyl) odonium trifluoromethanesulfonate and bis (4t-butylphenyl) odo-dimethylnonfluoro n Butanesulfonate, bis (4t-butylphenol) ode-dimethylperfluoro n-octanesulfonate, bis (4t-butylphenol) ode-dimethyl p-toluenesulfonate, bis (4-t) Butynolephene 2) odonium benzene snolephonate, bis (4-t-butyl phenol) odonium 2 trifluoromethylbenzenesulfonate, bis (4-t butyl phenol) odonium 4 trifluoromethylbenzene Sulfonate, bis (4t butylphenol) odonium 2,4 difluorobenzene Sulfonate, bis (4t butylphenol) odonium hexafluorobe Zen sulfonate, bis (4-t Buchirufue - Le) Yodoniumu 10-camphorsulfonate, Jifue - Ruyodoniu Mutifluoromethanesulfonate, diphenol-dumnonafluoro n-ptance norephonate, dipheninolenodium permphenolenoroleau n-octanes norephonate, diphenolenodonenium p tonoreensnore Honate, diphenyl benzoyl benzoate, diphenyl phenol 10-camphor phenol, diphenyl phenol 2 trifluoromethyl benzene sulfonate, diphenyl benzoyl phenol 4 trifluoromethyl benzene sulfonate Nitrate, diphenyl-nordone 2,4 diphenoleno-benzene benzene-norrephonate, diphenyl-hexa-hexahexoleno-benzene benzene-snorrenate, bis (4-trifluoromethylphenol) ode-dimethyltrifluoromethanesulfonate, bis ( 4 to Riflolo Thiophene) odo-dumnonafluoro-n-butanesulfonate, bis (4 trifluoromethylphene) odenium perfluoro-n-octanesulfonate, bis (4 trifluoromethylfruel) ) Eodo-pam p-toluenesulfonate, bis (4 trifluoromethylphenol) odonium benzenesulfonate, and bis (4 trifluoromethylphenyl) odonium-1 10-camphor sulfonate It is preferred that at least one type be.

[0083] [Formula 44]

In the formula (35), Q is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R′—O; R ′ is an alkylene group having 1 to 12 carbon atoms), R ²⁵ is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a carbon number. 6 to 12 halogen-substituted aryl groups.

[0085] The compound represented by the formula (35) includes N (trifluoromethylsulfo-loxy) succinimide, N- (trifluoromethylsulfo-loxy) phthalimide, and N- (trifluoromethylsulfo-loxy) diphen- Lumaleimide, N— (Trifluoromethylsulfo-loxy) bicyclo [2.2.1] Heptot-1-ene 2,3 dicarboximide, N— (Triflurimide O-methylsulfo-roxy) naphthylimide, N- (10-camphorsulfo-roxy) succinimide, N— (10-camphorsulfo-roxy) phthalimide, N— (10-force camphorsulfo-roxy) diphen-maleimide, N— (10— Camphorsulfo-roxy) bicyclo [2.2.1] hept-5-one-1,3-dicarboximide, N- (10-forcer-sulfo-roxy) naphthylimide, N- (n-octanesulfo-roxy) ) Bicro [2.2.1] hept-1-ene-1,3-dicanoleboxoxyimide, N- (n-octanesnorpho-roxy) naphthylimide, N- (p-toluenesulfo-roxy) bicyclo [2.2.1] Heptoh 5-ene-2,3-dicarboximide, N- (p-toluenesulfo-loxy) naphthylimide, N- (2-trifluoromethylbenzenesulfo- Roxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N— (2-trifluoromethylbenzenesulfo-roxy) naphthylimide, N— (4-trifluoromethyl Benzenesulfo-roxy) bicyclo [2.2.1] hept-5-ene-2,3-dicaroxyimide, N— (4-trifluoromethylbenzenesulfo-roxy) naphthylimide, N— Nsensulfo-roxy) bicyclo [2.2.1] hept-5-one-1,3-dicarboximide, N- (perfluorobenzenesulfo-roxy) naphthylimide, N— (1-naphthalene sulfo-roxy) ) Bicyclo [2.2.1] Heptot 5-ene-1,3-dicarboximide, N- (1-naphthalenesulfo-roxy) naphthylimide, N- (Nonafluoro-n-butanesulfo-roxy) bicyclo [2.2.1] Hept-5-ene-1,3-dicarboximide, N- (nonafluoro-n-butanesulfo-loxy) naphthylimide, N- (perfluoro-n-octanesulfo-loxy) bicyclo [2. 2.1] It is preferred that at least one selected from the group consisting of hept-5-one-1,3-dicarboximide and N- (perfluoro-n-octanesulfo-roxy) naphthylimide.

[0086] [Formula 45]

(36)

In the formula (36), R ^2b may be the same or different and each independently has 1 to 12 carbon atoms Linear alkyl group, branched alkyl group having 3 to 12 carbon atoms, cyclic alkyl group having 3 to 12 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 3 to 12 carbon atoms, or carbon number 7 to 12 aralkyl groups. Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, halogen, or a haloalkyl group having 1 to 12 carbon atoms.

 [0088] The compound represented by the formula (36) includes diphenyldisulfone, di (4-methylphenyl) disulfone, dinaphthyldisulfone, di (4tert-butylphenyl) disulfone, and di (4-hydroxyphenyl). ) Disulfone, di (3-hydroxynaphthyl) disulfone, di (4-phenolic phenole) disnorefone, di (2-phenolic phenole) disnorefone, and di (4-trifluoromethylphenyl) Preferably, at least one selected from the group consisting of disulfones.

 [0089]

(37)

In the formula (37), ′ may be the same or different and each is independently a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, A cyclic alkyl group having 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each of the substituents may be substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or an alkoxyl group having 1 to 12 carbon atoms.

[0091] The compound represented by the above formula (37) includes α (methylsulfo-roximino) phenylacetonitrile, at- (methylsulfo- luximino) -4-methoxyphenyl-acetonitrile, and α- (trifluoromethylsulfo- oximino) ) —Fue-L-acetonitrile, α- (Trifluoromethylsulfonyloximino) -4-methoxyphenylacetonitrile, α- (Ethylsulfo-Loximino) -4-Methoxyfure-Lacetonitrile, at- (Propyl Sulfo-Roxyimino) -4 Methylphen -Racetonitrile, and α (methylsulfo-roxyimino) -4-bromo-phenylacetonitrile group are preferably at least one selected from the group consisting of: [0092] [Formula 47]

ο, ⁰

 (38)

R ² co = R ²⁸

[0093] In the formula (38), may be the same or different and are each independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The number of carbon atoms of the halogenated alkyl group is preferably 1 to 5.

 The compound represented by the above formula (38) can be used as a monoisocyanouric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dibumoisocyanuric acid, trichloroisocyanuric acid, and tribromoisocyanuric acid. It is preferable that at least one kind is selected.

 [0094] [Formula 48])

In the formulas (39) and (40), R ²⁹ and R ³ ° each independently represent an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; cyclopentyl A cycloalkyl group having 3 to 12 carbon atoms such as a cyclohexyl group; a alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group or a propoxy group; a phenyl group, a tolyl group or a naphthyl group And preferably an aryl group having 6 to 10 carbon atoms. L ²⁹ and L ³ ° are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazido-4-sulfol group, a 1,2-naphthoquinonediazide-5-sulfol group, and a 1,2- 1,2-quinonediazide sulfol such as naphthoquinonediazido 6-sulfol group The groups can be mentioned as preferred. In particular, a 1,2 naphthoquinonediazide 1-4-sulfol group and a 1,2 naphthoquinonediazido 5-sulfol group are preferred. p is an integer of 1-3, q is an integer of 0-4, and l≤p + q≤5. J ²⁹ is a single bond, a polymethylene group having 2 to 4 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, a phenylene group having 6 to 10 carbon atoms, the following formula (41):

 [0096] [Formula 49]

[0097] A substituent represented by -R ^a -C (= 0) -R. One, -R ^a -C (= 0) one O—R ^b , one R ^a — C (= 0) —NH—R ^b —, or R ^c — O— R ^d — (where R ^a and R ^b represents an alkylene group having Yogu each independently a single bond or a 1 to 3 carbon atoms which may be the same or different, the sum of the carbon number of R ^a and R ^b is an 0 to 3; R ^e and R ^d is represents Yogu each independently a single bond or an alkylene group having 1 to 4 carbon atoms be the same or different, the total number of carbon atoms of R ^e and R ^d is 0-4 der Ru), Y ²⁹ is A hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, wherein X ²⁹ and X ³ ° are each represented by the following formula (42):

 [0098] [Formula 50]

(In the formula (42), each independently represents an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms; ³² is an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a carbon atom It is an alkoxyl group of numbers 1-3, and r is an integer of 0-3. )

 Is a group represented by

 [0100] As other compounds (B), bis (p-toluenesulfol) diazomethane, bis (2,4-dimethylphenylsulfol) diazomethane, bis (tert-butylsulfol-) diazomethane, bis (n- Bissulfo- such as butylsulfol-diazomethane, bis (isobutylsulfol-) diazomethane, bis (isopropylsulfol-) diazomethane, bis (n-propylsulfol-) diazomethane and bis (cyclohexylsulfol-) diazomethane; Ludazomethanes, 2- (4-methoxyphenyl) -1,4,6- (bistrichloromethyl) 1,3,5 triazine, 2- (4-methoxynaphthyl) 4,6— (bistrichloromethyl) 1, 3,5 Triazine, halogen containing tris (2,3 dibromopropyl) 1,3,5 triazine, tris (2,3 dibromopropyl) isocyanurate Toriajin derivatives, and the like.

 [0101] The component (B) can be used alone or in combination of two or more. In the composition of the present invention, the amount of component (B) used is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 20 parts by weight, and even more preferably from 1 to 15 parts by weight, per 100 parts by weight of the resist conjugate. Parts by weight. It is preferable that the ratio is in the above range because the sensitivity, the resolution, and the cross-sectional shape of the resist pattern are good.

 [0102] In the resist composition of the present invention, a crosslinking agent, a dissolution promoter, a dissolution controlling agent, a sensitizer, One or more kinds of various additives such as surfactants and the like can be added.

 [0103] [1] Crosslinking agent

 In the present invention, in order to increase the sensitivity, a carbon-carbon multiple bond group, a cyclopropyl group, an azide group, a poly (vinyl) group, an aryl group, a cinnamoyl group, a bulsilyl group, an epoxy group, a halogenated methyl group, a halogenated phenyl Compounds having a group or a resin can also be added, and in particular, compounds having a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated polyyl group, and a halogenated methyl group, Or a resin is preferred.

These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent is preferably 50 parts by weight or less, more preferably 25 parts by weight or less, per 100 parts by weight of the resist conjugate. It is at most 5 parts by weight, particularly preferably at most 5 parts by weight.

[2] Sensitizer

 The sensitizer absorbs the energy of the irradiated radiation and transfers the energy to the compound (B), thereby increasing the amount of radicals or cations generated. It is a component that improves sensitivity. Such sensitizers include, for example, a triphenylmethane-based leuco dye such as leuco crystal violet, leucomalachite green disclosed in U.S. Pat. No. 3,479,185, and erythrocycin. Photoreducing dyes such as jeosin Y, Michler's ketone and aminostyryl ketone disclosed in U.S. Patent No. 3,549,367, U.S. Patent No. 3,652,275, etc. Aromatic ketones such as benzophenone and biacetyl; ι8-diketones described in U.S. Pat. No. 3,844,790; indanones found in U.S. Pat. No. 4,162,162; Ketocoumarins disclosed in JP-A-52-112681, aminostyrene derivatives and aminopolybutadiene derivatives disclosed in JP-A-59-56403, and US Pat. No. 4,594,310. amino Polyyl heterocycles, julolidine heterocycles described in U.S. Pat. No. 4,966,830, pyromethene dyes described in JP-A-5-241338, pyrenes, phenothiazines, fluorenes, etc. Can be listed, but is not particularly limited.

 These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the resist conjugate.

[3] Surfactant

The surfactant is a component having an effect of improving the coatability, striation, developability as a resist, and the like of the resist composition of the present invention. As such a surfactant, any of a union type, cationic type, non-one type and amphoteric type can be used. Among these, preferred surfactants are nonionic surfactants. Nonionic surfactants have a higher affinity for the solvent used in the radiation-sensitive composition. Examples of nonionic surfactants include higher alkyl ethers of polyoxyethylene, higher alkyl ether ethers of polyoxyethylene, and higher fatty acids of polyethylene glycol. In addition to fatty acid diesters, etc., the following trade names are F-Top (manufactured by Gemcone Earth), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3LEM), Asahigard, Surflon (above, Asahi Glass ), KP (manufactured by Toho Chemical Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), and the like, but are not particularly limited thereto.

 The amount of the surfactant is preferably 2 parts by weight or less as an effective component of the surfactant per 100 parts by weight of the resist conjugate.

[4] Other additives other than the above-mentioned crosslinking agent, sensitizer, and surfactant

 Further, the resist composition of the present invention may contain one or more additives other than the above-mentioned crosslinking agents, sensitizers, and surfactants, as needed, as long as the object of the present invention is not impaired. More than one kind can be blended. Other additives include, for example, dissolution promoters, dissolution control agents, dyes, pigments, and adhesion aids. For example, it is preferable to mix a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation at the time of exposure can be reduced. Further, it is preferable to add an adhesion auxiliary agent, since the adhesion to the substrate can be improved. Further, other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, and the like, and specifically, 4-hydroxy-4'methylchalcone. Usually, it is prepared by dissolving each component in a solvent at the time of use to form a homogeneous solution, and then, if necessary, filtering the solution with a filter having a pore diameter of about 0.2 m or the like. In this case, the total solid content concentration in the homogeneous solution is usually 50% by mass or less, preferably 1 to 50% by mass, more preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.

[0107] As the solvent used in the preparation of the resist composition of the present invention, for example, ethylene glycol Honoré mono-methylol Honoré ether Honoré acetate, ethylene glycol Honoré monomethyl E Chino les ether Bruno rare Seteto, ethylene glycol Honoré mono over _n - Ethylene glycolone monoenolequinoleate, such as n-butinooleatenoleacetate and ethylene glycol monoenoate acetate; ethylene glycol monoene etherate, such as ethylene glycolone monomethinoleether and ethylene glycolone monoethyl ether Alkyl ethers; propylene glycol Propylene glycol monoalkyl ether acetates such as olemonomethinoleate enoleacetate, propylene glycol olemonoethino oleate enoate acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol oleno mono n-butyl ether acetate; Propylene glycol monoalkyl ethers such as monomethinole ether and propylene glycol monoethyl ether; Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; methyl acetate, acetic acid Aliphatic carboxylic acid esters such as ethyl, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and ethyl propionate; Methyl onate, 3-ethyl methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyethyl propionate, 3-methoxy-2-methylpropionate methyl pionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyla Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; Ratatones such as y-rataton can be exemplified, but are not particularly limited. These solvents can be used alone or in combination of two or more.

 The resist composition of the present invention may be irradiated with, or induced by, visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray and ion beam within a range that does not inhibit the object of the present invention. A compound having a cross-linking reactive group that causes a cross-linking reaction by a chemical reaction, a compound having a butyl group, an aryl group, a cinnamoyl group, a bursilyl group, an epoxy group, a chloromethyl group, a phenyl group, a Z- or a resin, can do. The compound having a cross-linking reactive group and the Z or resin are not particularly limited, and the compound and the Z or resin soluble in the alkaline aqueous solution may be combined with visible light and ultraviolet light.

, Excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam irradiation, or a crosslinking reactive group introduction reagent that causes a crosslinking reaction by a chemical reaction induced by the irradiation under a base catalyst. Compound and Z or polymer, or Derivatives thereof. The term "crosslinking-reactive group-introducing agent" used herein refers to a compound having a crosslinking-reactive group, such as an acid, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkylno, or a ride. Of these, acid salt products are particularly preferred. The crosslinking reactive group is a vinyl group, an aryl group, a cinnamoyl group, a bursilyl group, an epoxy group, a methyl halide group, or a phenyl halide group. These may be used as a mixture of one or more.

 [0109] The resist composition of the present invention is usually compounded at 40 to 99.998% by weight of the resist compound (A), 0.001 to 10% by weight of the compound (B), and other components (C) in the total solid content. 0.001 to 50% by weight, preferably 90 to 99.99% by weight, and the compound (B) O. 001 to: LO weight are more preferable. Within the above range, the performance such as resolution is excellent. In the case where the compound (B) functions as a negative resist without the compound (B) in the total solid content, 100% by weight of the resist conjugate (A) is particularly preferable.

 [0110] In the present invention, the resist substrate is a resist substrate on which a resist film made of the resist composition is formed, and the pattern-formed substrate is a substrate on which the resist film on the resist substrate is exposed. This is a substrate having a patterned resist film obtained by development. Further, “pattern forming material” refers to a composition formed on a resist substrate and capable of forming a pattern by irradiation of light, extreme ultraviolet (EUV), electron beam, or radiation, and is synonymous with “resist film”. . The “patterned wiring board” is a substrate having patterned wirings obtained by etching a pattern forming substrate.

 [0111] As a method of forming a resist pattern using the resist composition of the present invention, a step of applying the resist composition on a substrate to form a resist film, a step of heat-treating the resist film as necessary, Exposing the resist film to visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, or ion beam power. And then subjecting the exposed resist film to development using an alkali developing solution.

[0112] To form a resist pattern, first, the resist composition of the present invention is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, casting coating, or roll coating. To form a resist film. As needed Then, a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance.

 [0113] Next, the coated substrate is heated as necessary. The heating conditions are preferably 20 to 250 ° C, more preferably 20 to 150 ° C, depending on the composition of the radiation-sensitive composition. Heating is preferable because the adhesiveness of the resist to the substrate may be improved. Next, the resist film is exposed to a desired pattern by any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam. Exposure conditions and the like are appropriately selected according to the composition of the radiation-sensitive composition and the like. In the present invention, in order to stably form a high-precision fine pattern in exposure, it is preferable to perform heating after radiation irradiation. The heating conditions are preferably 20 to 250 ° C, more preferably 20 to 150 ° C, depending on the composition of the radiation-sensitive composition.

Next, a predetermined resist pattern is formed by developing the exposed resist film with a resist soluble developer. As the resist friendly溶現image solution, the resist solution same as can be used as the solvent was adjusted, for example, ethylene glycol monomethyl ether § cetearyl over preparative, ethylene glycol Honoré monomethyl E Chino les ether Honoré acetate, ethylene glycol Honoré monomethyl over _n propyl Ethylene glycolone monoethylene ether acetates (PGMEA), propylene glycol monoethyl ether, such as ethylene glycolone monooleate acetate and ethylene glycolone monooleate acetate, etc. acetate, propylene glycol monomethyl over n-propyl ether acetate, propylene glycol monomethyl over _n - propylene glycol monoalkylene ether acetates such as butyl acetate; methyl lactate E Lactate esters such as (EL), n-propyl lactate, n-butyl lactate, n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, Aliphatic carboxylic acid esters such as methyl propionate and ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyethyl ethyl pionate, 3-methoxy-2 Methyl methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-butyl butyl propionate, 3-methoxy-3-methyl butyl butyrate, methyl acetate acetate, pyruvate Other esters such as methyl and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 41-heptanone and cyclohexanone; N, N— Amides such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; ratatones such as γ-ratathone; These solvents can be used alone or in combination of two or more.

 [0115] Further, an appropriate amount of the surfactant can be added to the resist-soluble developer.

 This is preferable because the wettability of the developer to the resist can be increased. After forming a resist pattern, etching is performed to obtain a patterned wiring board. The etching can be performed by a known method such as dry etching using a plasma gas.

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

[0116] Further, the resist pattern can be stripped with an organic solvent having higher solubility than the resist soluble developer. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may have a small-diameter through hole, which is suitable for a multilayer wiring board.

 The wiring substrate obtained by using the resist composition of the present invention can also be formed by a method of forming a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.

 Example

 Hereinafter, embodiments of the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.

 <Synthesis Example 1> to <Synthesis Example 28>

The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. Tables 1 and 2 show the results of these analyses. In Table 1, the number of atoms of each compound is defined as the value of the descriptive formula. The values of the weight percentages of the elements are shown as calculated and measured values, and the values of F = total number of atoms Z (total number of carbon atoms and total number of oxygen atoms) are shown. Table 2 shows the NMR measurement results.

 [0118] Synthesis Example 1: Synthesis of compound (26-1)

Triethyl methanetriisocyanate (ΤΡΜΤΙ) in ethyl acetate Ζ Monochrome mouth benzene (7 OZ3 (weight ratio)) 27% by weight solution (Bayer Desmodur RE, NCO equivalent: 441, Non-volatile content: 27% ⁰ / ₀ ) 2. A solution prepared by adding 3 ml of dimethimecetamide (DMAc) to 21 g was added dropwise. Using a funnel, slowly add a solution of P-aminophenol (AP) O. 55 g / 5 mmol (1.0 equivalent) to 5 ml of DMAc. The mixture was added dropwise and stirred at room temperature for 1 hour. Further, 2.12 g (22.5 mmol) of Atiroku Irkoku Ride (a reagent manufactured by ACROS) and 2.29 g of triethylamine (a reagent manufactured by Kanto Chemical Co., Ltd.) were slowly added dropwise, followed by stirring at room temperature for 3 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDM Ac = 3Z4Z100 (volume ratio), and a main component was taken out. Finally, drying under reduced pressure was carried out to obtain 0.89 g of the compound (26-1).

 [0119] Synthesis Example 2: Synthesis of compound (26-2)

Acetic TPMTI Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. using a dropping funnel a solution of example mosquitoes卩the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) Was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the crystals separated by filtration were dissolved in acetone, and then added again to a large amount of water for crystallization to obtain 0.5 g of a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane Z, ethyl acetate Z, DMAc = 3Z4Z100 (volume ratio), and the main component was taken out. Next, 0.5 g of the main component, 3.02 g (25 mmol) of 3-bromopropene (ACROS reagent), 3.5 g (25 mmol) of potassium carbonate (reagent manufactured by Kanto Idani Gaku Co., Ltd.), sodium iodide (Reagent manufactured by Kanto-Danigaku Co., Ltd.) 0.036 g (0.25 mmol) and 30 ml of acetone were added, and the mixture was stirred at 55 ° C. for 24 hours in a nitrogen stream. After completion of the reaction, the salt was filtered, the solvent was concentrated, and then purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDMAc = 3Z4Z100 (volume ratio) to remove the main component. Finally, drying under reduced pressure was performed to obtain 0.86 g of the compound (26-2). [0120] Synthesis Example 3: Synthesis of compound (26-3)

Acetic TPMTI Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. using a dropping funnel a solution of example mosquitoes卩the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) Was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the crystals separated by filtration were dissolved in acetone, and then added again to a large amount of water for crystallization to obtain 0.5 g of a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane Z, ethyl acetate Z, DMAc = 3Z4Z100 (volume ratio), and the main component was taken out. Next, 0.5 g of the main component, 1.8 g (92.5 mmol) of epichlorohydrin and 0.73 g of 2-propanol were charged, and the mixture was heated to 40 ° C and uniformly dissolved. 0.32 g of an aqueous solution of sodium hydroxide was added dropwise over 90 minutes. During this period, the temperature was gradually raised, and after the completion of the dropwise addition, the temperature in the system was adjusted to 65 ° C., followed by stirring for 30 minutes. Next, excess epichlorohydrin and 2-propanol were distilled off from the product under reduced pressure, dissolved in 2 g of methyl isobutyl ketone, and 0.02 g of a 48.5% by weight aqueous sodium hydroxide solution was added. The mixture was stirred at ° C for 1 hour. Thereafter, an aqueous solution of sodium phosphate monobasic was added to the reaction solution to neutralize excess sodium hydroxide, and the solution was washed with water to remove by-product salts. Next, methyl isobutyl ketone was completely removed, and finally, drying under reduced pressure was performed to obtain 0.22 g of a compound (26-3).

 [0121] Synthesis Example 4: Synthesis of compound (26-4)

Acetic TPMTI Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. using a dropping funnel a solution of example mosquitoes卩the DMAc3ml to 2 lg, APO. 55g / 5mmol (l. 0 equivalents ) Was slowly added dropwise to a 5 ml solution of DMAc, and the mixture was stirred at room temperature for 1 hour. Further, 3.24 g (25 mmol) of bromoke-containing methane and 2.29 g of triethylamine (a reagent manufactured by Kanto-Danigaku Co., Ltd.) were slowly dropped, and the mixture was stirred at room temperature for 3 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDMAc = 3/4 Z100 (volume ratio) to extract the main component. Finally, drying under reduced pressure was performed to obtain 0.67 g of the compound (26-4).

 [0122] Synthesis Example 5: Synthesis of compound (27-1)

TPMTI acetate Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. 2 lg and 3, 5-dihydroxy-benzyl alcohol (DHBA) O. 70g / 5mmol ( l. 0 eq) And 4.24 g (45. Ommol) of the compound were reacted in the same manner as in Synthesis Example 1 to obtain 1.02 g of a compound (27-1).

[0123] Synthesis example 6: Synthesis of compound (27-2)

TPMTI acetate Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. 2 lg and DHBAO. 70g / 5mmol (l. 0 eq), and the 3-bromo-propene 6. 04g (50m mol) Was reacted in the same manner as in Synthesis Example 2 to obtain 0.99 g of a compound (27-2).

[0124] Synthesis Example 7: Synthesis of compound (27-3)

TPMTI acetate Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. 2 lg and DHBAO. 70g / 5mmol (l. 0 eq), and E peak chlorohydrin 7. 2 g (185. Om mol) was reacted in the same manner as in Synthesis Example 3 to obtain 0.55 g of compound (27-3).

[0125] Synthesis Example 8: Synthesis of compound (27-4)

TPMTI acetate Echiru Z monochrome port benzene (70Z3 (weight ratio)) 27 wt _^0/0 solution 2. 2 lg and DHBAO. 70g / 5mmol (l. 0 eq), and bromochloromethane 6. 48 g of (50 mm ol) The reaction was carried out in the same manner as in Synthesis Example 4 to obtain 0.67 g of compound (27-4).

[0126] Synthesis Example 9: Synthesis of compound (28-1)

 27% by weight solution of tris (phenylisosinate) thiophosphate (TIPTP) in ethyl acetate Z-clozen benzene (70Z3 (weight ratio)) (Desmodule RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content: 27% by weight) 2 The reaction of 91 g with APO. 55 g / 5 mmol (l. 0 eq.) And acryloyl chloride 2.12 g (22.5 mmol) was carried out in the same manner as in Synthesis Example 1 to give 0.62 g of compound (28-1). Got.

[0127] Synthesis Example 10: Synthesis of compound (28-2)

Acetic TIPTP Echiru Z black port benzene (70Z3 (weight ratio)) 27 wt% solution (Bayer Desmodur RFE, NCO equivalent: 581, nonvolatile content: 27 weight _^0/0). 2. 91g and APO 55 g / 5 mmol (l. 0 equivalents) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.65 g of compound (28-2).

[0128] Synthesis Example 11: Synthesis of Compound (28-3)

Acetic TIPTP Echiru Z black port benzene (70Z3 (weight ratio)) 27 wt% solution (Bayer Desmodur RFE, NCO equivalent: 581, nonvolatile content: 27 weight _^0/0). 2. 91g and APO 55 The reaction of g / 5 mmol (1.0 equivalent) and 1.8 g (92.5 mmol) of epichlorohydrin was carried out in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (28-3).

 Synthesis Example 12: Synthesis of compound (28-4)

Acetic TIPTP Echiru Z black port benzene (70Z3 (weight ratio)) 27 wt% solution (Bayer Desmodur RFE, NCO equivalent: 581, nonvolatile content: 27 weight _^0/0) 2.91 g and APO.55 g / 5mmol ( l.0 eq.) and 3.24 g (25 mmol) of bromochloromethane were reacted in the same manner as in Synthesis Example 4 to obtain 0.61 g of compound (28-4).

 [0130] Synthesis Example 13: Synthesis of compound (29-1)

 A solution prepared by adding 0.6 ml of polymethylene polyisocyanate (MDI) (Sumidur 44 V20 manufactured by Sumika Bayer Urethane Co., Ltd., NCO equivalent: 135, non-volatile content: 100% by weight) to 5 g of DM Ac in 0.62 g was dropped into a funnel. APO. 55 g / 5 mmol (1.0 eq) and 2.12 g (22.5 mmol) of Atari iris mouth were reacted in the same manner as in Synthesis Example 1 to obtain 0.55 g of compound (29-1). Was.

 Synthesis Example 14: Synthesis of Compound (29-2)

MDI (manufactured by Sumika Bayer Urethane Co. Sumidur 44V20, NCO equivalent: 135, nonvolatile content: 100 weight _^0/0) 0.62 g and APO.55g / 5mmol (l.0 equiv), and 3-Buromopurobe down 3.02 g (25 mmol) was reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (29-2).

 [0132] Synthesis Example 15: Synthesis of compound (29-3)

MDI (manufactured by Sumika Bayer Urethane Co. Sumidur 44V20, NCO equivalent: 135, nonvolatile content: 100 weight _^0/0) 0.62 g and APO.55g / 5mmol (l.0 equiv), and E peak chlorohydrin 1.8 g (92.5 mmol) was reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (29-3).

 [0133] Synthesis Example 16: Synthesis of compound (29-4)

MDI (manufactured by Sumika Bayer Urethane Co. Sumidur 44V20, NCO equivalent: 135, nonvolatile content: 100 weight _^0/0) 0.62 g and APO.55g / 5mmol (l.0 equiv), and bromo-chloro-methane 3.24g (25 mmol) was reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (29-4). Synthesis Example 17: Synthesis of compound (24-1)

Tolylene iso Xia acetate E Chi le 75 weight trimethylolpropane § duct of sulfonate (TDITMP) _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight ⁰ / ₀ ) 1.58 g, the reaction of APO. 55 g / 5 mmol (1.0 equivalent) and attarylyl chloride 2.12 g (22.5 mmol) was carried out in the same manner as in Synthesis Example 1 to give 0.58 g of compound (24-1). Obtained.

 [0135] Synthesis Example 18: Synthesis of compound (24-2)

TDITMP acetate Echiru 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight _^0/0) and 1.58g, APO.55g / 5mmol (l.0 Equivalent) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (24-2).

 [0136] Synthesis Example 19: Synthesis of compound (24-3)

TDITMP acetate Echiru 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight _^0/0) and 1.58g, APO.55g / 5mmol (l.0 Eq.) And 1.8 g (92.5 mmol) of epichlorohydrin were reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (24-3).

 [0137] Synthesis Example 20: Synthesis of compound (24-4)

TDITMP acetate Echiru 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur L75, NCO equivalent: 324, nonvolatile content: 75 weight _^0/0) and 1.58g, APO.55g / 5mmol (l.0 Equivalent) and 3.24 g (25 mmol) of bromochloromethane were reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (24-4).

 [0138] Synthesis Example 21: Synthesis of compound (25-1)

Hexamethylene di iso Xia methoxypropyl § cetearyl one preparative Z xylene 75 weight _^0/0 solution of biuret of sulfonate (HDI) (manufactured by Sumika Bayer Urethane Co. Sumidur N75, NCO equivalent: 255, nonvolatile content: The reaction of 1.31 g (75% by weight), 55 g / 5 mmol (1.0 equivalent) of APO, and 2.12 g (22.5 mmol) of Atari or ilkopen chloride was carried out in the same manner as in Synthesis Example 1 to give the compound (25- 1) 0.58 g was obtained.

[0139] Synthesis Example 22: Synthesis of compound (25-2) HDI of methoxypropyl acetate Z xylene 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur N75, NCO equivalent: 255, nonvolatile content: 75 weight _^0/0). 1. 31 g and, APO 55 g / 5 mmol (l. 0 equivalent) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (25-2).

[0140] Synthesis Example 23: Synthesis of Compound (25-3)

HDI of methoxypropyl acetate Z xylene 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur N75, NCO equivalent: 255, nonvolatile content: 75 weight _^0/0). 1. 31 g and, APO 55 g / 5 mmol (1.0 equiv.) and 1.8 g (92.5 mmol) of epichlorohydrin were reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (25-3).

[0141] Synthesis example 24: Synthesis of compound (25-4)

HDI of methoxypropyl acetate Z xylene 75 weight _^0/0 solution (manufactured by Sumika Bayer Urethane Co. Sumidur N75, NCO equivalent: 255, nonvolatile content: 75 weight _^0/0). 1. 31 g and, APO 55 g / 5 mmol (l. 0 equivalent) and 3.24 g (25 mmol) of bromochloromethane were reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (25-4).

[0142] Synthesis Example 25: Synthesis of compound (191)

Tolylene iso Xia sulfonates of Isoshianureto (TDI) of butyl acetate 50 wt _^0/0 solution (Dainippon Ink and Chemicals Ltd. BURNOCK D-800, NCO equivalent: 592, nonvolatile content: 51 weight _^0/0) and 2. 8 9 g, The reaction of APO. 55 g / 5 mmol (l. 0 eq.) And 2.12 g (22.5 mmol) of Atari Irkokulide was carried out in the same manner as in Synthesis Example 1 to obtain 0.58 g of compound (19-1). Was.

Synthesis Example 26: Synthesis of compound (192)

 TDI butyl acetate 50% by weight solution (Dainippon Ink Kogyo Burnock D-800, NCO equivalent: 592, non-volatile content: 51% by weight) 2.89 g, APO. 55 g / 5 mmol (l. 0 equivalent), and The reaction of 3.02 g (25 mmol) of 3-bromopropene was carried out in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (19-2).

Synthesis Example 27: Synthesis of compound (193)

TDI butyl acetate 50% by weight solution (Dainippon Ink Kogyo Burnock D-800, NCO equivalent: 592, non-volatile content: 51% by weight) 2.89 g, APO. 55 g / 5 mmol (l. 0 equivalent), and Reaction of 1.8 g (92.5 mmol) of bipiclorhydrin was carried out in the same manner as in Synthesis Example 3. 0.65 g of the product (19-3) was obtained.

[0145] Synthesis Example 28: Synthesis of compound (194)

 2.89 g of a 50 wt% solution of TDI in butyl acetate (Dainippon Ink Industries, Inc., Vernock D-800, NCO equivalent: 592, non-volatile content: 51 wt%), APO.55 g / 5 mmol (l.0 equivalent), and The reaction of 3.24 g (25 mmol) of bromochloromethane was reacted in the same manner as in Synthesis Example 4 to give the compound

(19-4) 0.58 g was obtained.

[Table 1]

^ Table 1

 Indication formula 1—decimal value

 Synthesis example Compound Molecular weight 3 赚 F

 C H CI N 0 P S C H CI N 0 P S C H

1 26-1 49 40 6 9 856.9 68.68 4J1 9.81 16.80 68.66 4J3 2.60

2 26-2 49 46 6 6 814.9 72.22 5.69 10.31 11.78 72.20 5.65 2.49

3 26-3 49 46 6 9 862.9 68.20 5.37 9.74 16.69 68.10 5.38 2J5

4 26-4 43 37 3 6 6 840.2 61.47 4.44 12.66 10.00 11.43 61.32 4.42 2.57

5 27-1 61 49 3 18 1112.1 65.88 4.44 3.78 25.90 65.70 4.46 3.05

6 27-2 61 61 3 12 1028.2 71.26 5.98 4.09 18.67 71.26 6.00 2.80

7 27-3 61 61 3 18 1124.2 65.17 5.47 3.74 25.62 65.00 5.43 3.33

8 27-4 49 43 6 3 12 1078.6 54.56 4.02 19.72 3.90 17.80 54.20 3.99 3.05

9 28-1 48 39 6 12 1 1 954.9 60.37 4.12 8.80 20.11 3.24 3.36 60.40 4.08 2.97

10 28-2 48 45 6 9 1 1 913 63.15 4.97 9.21 15.77 3.39 3.51 63.10 4.95 2.82

11 28-3 48 45 6 12 1 1 960.9 59.99 4J2 8J5 19.98 3.22 3.34 59.32 4.70 3.14

12 28-4 42 36 3 6 9 1 1 938.2 53.77 3.87 11.34 8.96 15.35 3.30 3.42 53.70 3.85 2.97

13 29-1 50 42 6 9 870.9 68.96 4.86 9.65 16.53 68.86 4.82 2.61

14 29-2 50 48 6 6 829 72.45 5.84 10.14 11.58 72.35 5.81 2.50

15 29-3 50 48 6 9 877 68.48 5.52 9.58 16.42 68.40 5.50 2.76

16 29-4 44 39 3 6 6 854.2 61.57 4.60 12.45 9.84 11.24 61.57 4.57 2.58

17 24-1 60 59 9 15 1146.2 62.87 5.19 11.00 20.94 62.76 5.23 3.18

18 24-2 60 65 9 12 1104.2 65.26 5.93 11.42 17.39 65.26 5.90 3.04

19 24-3 60 65 Θ 15 1152.2 62.54 5.69 10.94 20.83 62.54 5.65 3.31

20 24-4 54 56 3 9 12 1129.4 57.43 5.00 9.42 11.16 17.00 59.97 5.18 3.19

21 25-1 50 65 9 11 968.1 62.03 6.77 13.02 18.18 62.03 6.76 3.46

22 25-2 50 71 9 8 926.2 64.84 7.73 13.61 13.82 64.81 7.70 3.29

23 25-3 50 71 9 11 974.2 61.65 7.35 12.94 18.01 61.63 7.32 3.62

24 25-4 44 62 3 9 8 951.4 55.55 6.57 11.18 13.25 13.45 55.25 6.50 3.50

25 19-1 54 45 9 12 1012 64.09 4.48 12.46 18.97 64.22 4.44 2.86

26 19-2 54 51 9 9 970.04 66.86 5.30 13.00 14.84 66.80 5.28 2.73

27 19-3 54 51 9 12 1018 63.71 5.05 12.38 18.86 63.70 5.01 3.00

28 19-4 48 42 3 9 9 995.3 57.93 4.25 10.69 12.67 14.47 57.96 4.25 2.85

施例 1〜36、比較例 1

Examples 1-36, Comparative Example 1

After making the resist compound (A), compound (B) and the solvent shown in Table 3 into a homogeneous solution, the pore size was 0 The solution was filtered through a 2 m Teflon membrane filter to prepare a resist composition. The obtained resist composition was spin-coated on a silicon wafer to form a resist film. Table 5 shows the film forming properties of each of the obtained resist films.

[0149] The resist was spin-coated on a clean silicon wafer, and then subjected to a pre-exposure bake (PB) in an oven to form a 0.2-m-thick resist film. The resist coating was exposed to i-line at a wavelength of 365 nm in Examples 1 to 32, and exposed to an electron beam in Examples 33 to 36, and Comparative Example 1, and then exposed to an electron beam in an oven and then beta-exposed. 4 tables). Developing was performed at 23 ° C for 5 seconds with DMA c by the stationary method. Thereafter, the resultant was dried to form a negative resist pattern. Each of the obtained resist patterns was evaluated by the following method. Table 5 shows the evaluation results.

[0150] (1) Compound safety solvent solubility test

 A solubility test of the resist compound (A) in a safe solvent was performed at 23 ° C. The solubility in the solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethyl lactate and most soluble was evaluated according to the following criteria.

 A: 5% by weight or more dissolved

 B: 0.1% by weight or more to less than 5% by weight dissolved

 C: Dissolution force

 (2) Evaluation of film formability of resist film

 The resist composition was spin-coated on a silicon wafer with a spin coater to form a resist film, which was then heated on a hot plate at 110 ° C for 60 minutes, and the resist coating on a 6-inch silicon wafer was evaluated according to the following criteria.

 A: Good surface properties

 C: Partly whitened or uneven on the surface

 (3) resist pattern evaluation

 (S—DS / z mL & S

The resist pattern after development was observed with an optical microscope to confirm the formation of a 5 μm line and space, and evaluated according to the following criteria. A: Confirm

 C: Not confirmed

(3-2) 100nmL & S

 After the development, the resist pattern was observed with an electron microscope, and the presence or absence of the formation of line and space of IOOnmL & S was confirmed.

 A: Confirm

 C: Not confirmed

[Table 3]

 Table 3-2

 Compound (A) Compound (B) Solvent

 Comparative example

 Type Amount (g) Type Amount (g) Type Amount (g)

1 C-1 1 1 None 0 S-5 18.9 [0152] Compound (A)

 C-l: Calixresorcinarene derivative (Production method: JP-A-9-236919)

 [Formula 51]

[0153] Compound (B)

 R-l: Irgacure 907 (2-methyl-1 [(4-methylthio) phenyl] 2 morpholinopropane-1-one, Chinoku, manufactured by Specialty Chemicals)

 Solvent

 S-1: Propylene glycol monomethyl monoacetate (Tokyo Chemical Industry Co., Ltd.)

 S-2: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

 S-3: Ethyl lactate (Kanto Chemical Co., Ltd.)

 S-4: N, N dimethylacetamide (Kanto Iridaku Co., Ltd.)

 S-5: Methylene chloride (Kanto Chemical Co., Ltd.)

 S-1 / S-3: S-1 / S-3 (4/10 (weight ratio)) mixed solvent

[0154] [Table 4]

Table 4 1

 Pre-exposure bake (PB) exposure amount Post-exposure bake Example

 Temperature (° c) Time (mJ / cm2) Temperature (¾) Time ec)

1 100 600 5 280 150 600

2 100 600 5 280 150 600

3 100 600 5 280 150 600

4 100 600 5 280 150 600

5 100 600 5 280 150 600

6 100 600 5 280 150 600

7 100 600 5 280 150 600

8 100 600 5 280 150 600

9 100 600 5 280 150 600

10 100 600 5 280 150 600

1 1 100 600 5 280 150 600

12 100 600 5 280 150 600

13 100 600 5 280 150 600

14 100 600 5 280 150 600

15 100 600 5 280 150 600

16 100 600 5 280 150 600

17 100 600 5 280 150 600

18 100 600 5 280 150 600

19 100 600 5 280 150 600

20 100 600 5 280 150 600

21 100 600 5 280 150 600

22 100 600 5 280 150 600

23 100 600 5 280 150 600

24 100 600 5 280 150 600

25 100 600 5 280 150 600

26 100 600 5 280 150 600

27 100 600 5 280 150 600

28 100 600 5 280 150 600

29 100 600 5 280 150 600

30 100 600 5 280 150 600

31 100 600 5 280 150 600

32 100 600 5 280 150 600 Table 4 I 2

 Pre-exposure bake (PB) Exposure amount Post-exposure bake Example

 Temperature (° c) Time (uC / cm2) Temperature (° c) Time (sec)

33 100 600 300 150 600

34 100 600 300 150 600

35 100 600 300 150 600

36 100 600 300 150 600 Table 4-3

 Pre-exposure bake (PB) Exposure amount Post-exposure bake Comparative example

 Temperature (° c) Time (uC / cm2) Temperature (° c) Time (sec)

1 150 600 300 150 600 No. -1

Example Growth 14 5 // mL & S

1 A A A

2 A A A

3 A A A

4 A A A

5 A A A

6 A A A

7 A A A

8 A A A

9 A A A

10 A A A

11 A A A

12 A A A

13 A A A

14 A A A

15 A A A

16 A A A

17 A A A

18 A A A

19 A A A

20 A A A

21 A A A

22 A A A

23 A A A

24 A A A

25 A A A

26 A A A

27 A A A

28 A A A

29 A A A

30 A A A

31 A A A

32 A A A 5-2 Example Solubility test Film forming property 100nmL & .S

33 A A A

34 A A A

35 A A A

36 A A A Table 5-1 3 Comparative example Solubility test 1 Film formability 100nm & S

1 C C C

Claims

 The scope of the claims  [1] A resist composition comprising at least one resist compound (A) that satisfies all of the conditions (a) to (d).  (a) Visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam power. It has at least one crosslinkable reactive group in the molecule.  (b) The molecule has at least one functional group selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.  (c) Molecular weight force: 00-5000.  (d) It has a branched structure.  [2] The resist composition according to [1], wherein the resist compound (A) has two or more crosslinking reactive groups in a molecule.  [3] The resist composition according to claim 1 or 2, wherein the branched structure satisfies at least one of the following conditions (1) to (5).  (1) It has a tertiary carbon atom or tertiary nitrogen atom not included in the cyclic structure.  (2) It has a quaternary carbon atom.  (3) It contains at least one aromatic or aliphatic ring having three or more substituents.  (4) It has a tertiary phosphorus atom.  (5) It contains at least one isocyanurate ring. [4] The resistive tie (A) is  The resist composition according to any one of claims 1 to 3, wherein F≤5 (where F represents the total number of atoms Z (the total number of carbon atoms and the total number of oxygen atoms)). [5] The cross-linking reactive group of the resist compound (A) is selected from the group consisting of a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenyl group, and a methylphenol group. The resist composition according to claim 1, wherein the composition is at least one species. [6] The cross-linking reactive group of the resist compound (Α) is at least one selected from the group consisting of a carbon-carbon multiple bond group, an epoxy group and a methyl halide group. of! Or a resist composition according to any one of the preceding claims. [7] The resist compound (A) has at least one cross-linking reactive group on each of the branched molecular chains in the branched structure, and has an urea bond, a urethane bond, 7. The resist composition according to claim 1, which has at least one member selected from the group consisting of an amide bond and an imide bond. [8] The resist compound (A) has at least one cross-linking reactive group in each of the branched molecular chains in the branched structure, and has a urea bond and a urethane bond strength in each of the molecular chains. The resist composition according to any one of claims 1 to 7, comprising at least one member selected from the group consisting of: [9] The resist composition according to any one of [1] to [8], wherein the resist compound (A) has a nitrogen content of 30% by mass. [10] The resist composition according to any one of claims 1 to 9, which is a compound represented by the following formula (1):  [Chemical 1]

[In the formula (1), X is the following formula (I): [Chemical 2]

Represented by the formula (1) has at least 3 or more,  E is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;  s, t, and u each independently represent an integer of 0 to 3, and a plurality of E, X, Z, and Y may be the same or different. (In the above formula (I), R ¹ is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms. To 12 one-branched alkyl radicals, which are selected substituents;  Α is a hydrogen atom or a substituent selected from the group consisting of an aryloxy group, an atariloyloxy group, a glycidyloxy group and a chloromethyloxy group, and at least one of A is an aryloxy group, Atalyloyloxy, glycidyloxy, and chloromethyloxy groups which are selected substituents;  Ar is an aromatic hydrocarbon group having 6 to 12 carbon atoms;  Y is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, a substituted alkylene group having 1 to 12 carbon atoms, or a single bond;  Z represents a single bond or a substituent selected from the group consisting of O, —S, and —NH;  al is an integer from 1 to 9;  rl is an integer from 0 to 8;  al + rl≤9 n is 1. However,

A, Ar, al, and rl may be the same or different. )] The resist composition according to claim 0, wherein the compound of the formula (1) is a compound represented by the formula (4) or (6). [Formula 3] ( Five;

,  (6)  0 X X (In the formulas (4) to (6), X and E are the same as described above.)  (10) The resist composition according to any one of (9), which is a compound represented by the following formula (2). [Formula 4] GH-X (2) [In the formula (2), X is the same as described above, and a plurality of Xs may be the same or different.

Is a characteristic group derived from the structure of  X is bonded to three or more aromatic or aliphatic rings in formulas (i) to (V),  V represents an integer of 3 to 15. (In the above formulas (i) to (ii), R is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon R ³ is a hydrogen atom, a hydroxyl group, a non-cyclic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic carbon group having 3 to 12 carbon atoms. A hydrogen group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi): [Formula 6]

(In the formula (vi), a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms) And r is an integer of 0 to 4, k is an integer of 1 to 7, and a plurality of R and r are the same. In the formulas (iv) to (v), E ′ may be the same or different and each independently represents a single bond, a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, A divalent cyclic hydrocarbon group having 3 to 12 carbon atoms or 1 to 12 carbon atoms X represents a substituted alkylene group; }] [13] The resist composition according to claim 12, wherein the compound of the formula (2) is a compound represented by the following formula (9).  [Formula 7]

(In the formula (9), X and R ² are the same as described above.) 14. The resist composition according to claim 12, wherein the compound of the formula (2) is a compound represented by the following formula (10).  [Formula 8]

(In the formula (10), X is the same as described above.)  13. The resist composition according to claim 12, wherein the compound of the formula (2) is a compound represented by the following formula (11). [Formula 9]

(In the formula (11), X and k are the same as described above.) [16] The resist composition according to claim 12, which is a compound represented by the following formula (12):  [Formula 10]

(In the formula (12), X is the same as described above.) [17] The resist composition according to claim 12, which is a compound represented by the following formula (13):  [Formula 11]

(In the formula (13), X is the same as described above.) [18] The resist composition according to claim 12, which is a compound represented by the following formula (14): [Formula 12]

(In the formula (14), X is the same as described above.) [19] The resist composition according to any one of claims 1 to 9, wherein the resist conjugate (A) is a compound represented by the following formula (3).  [Formula 13]

[In the formula (3), R ³ is a group consisting of a hydrogen atom, an acyclic hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkyl group having 1 to 12 carbon atoms. X, E ² and k are the same as described above;  B is the following formula (vi): [Formula 14]

(In the formula (vi), X and E ² are the same as described above.) And E ¹ and E ¹ ′ may be the same or different and each independently represents a single bond or a divalent hydrocarbon group having 1 to 11 carbon atoms. However, the total number of carbon atoms of E ¹ and E ¹ is 0 to: L 1. J is a group selected from —O—, —S—, —NH— and a single bond. However, multiple B,

E ¹ ′, E ² , and J may be the same or different. ] [20] The resist composition according to claim 19, which is a compound represented by the following formula (8):  [Formula 15]

(In equation (8),

XJ and k are the same as described above, and a plurality of R ³ E ² XJs may be the same or different.  10. The resist composition according to claim 19, which is a compound represented by the following formula (7):  [Formula 16]

(In the formula (7), E ² X and k are the same as described above.) 22. The resist composition according to claim 102, wherein V in each of the formulas (1) to (14) is represented by the following formula (II) or (III).  [Formula 17]

(II) (III) (In the formula (II) or (III), A is the same as described above, and m is an integer of 1-2) [23] The resist composition according to any one of claims 1 to 22, comprising at least two kinds of the resist compound (A).  [24] Surface radiation, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam power 24. The resist composition according to V, wherein the resist composition contains a compound (B) that generates a cation.  [25] A compound having at least one selected from the group consisting of a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenyl group, and a halogenated methyl group, or The resist composition according to any one of claims 1 to 24, comprising a fat.  [26] In the total solid content of the resist composition, the resist conjugate (A) is 40 to 99.998% by weight, the compound (B) O. 001 to 10% by weight, and other components (C) O. 26. The resist composition according to claim 24, wherein the content is 001 to 50% by weight.  27. The resist composition according to claim 24 or 25, wherein the resist compound (A) is 90-99.999% by weight and the compound (B) O.001-: LO% by weight in the total solid content of the resist composition. Resist composition.  [28] The resist compound (A) is 100% by weight based on the total solid content of the resist composition. The resist composition according to any one of ~ 23! [29] A resist compound represented by the following formula (1):  [Formula 18]

[In the formula (1), X is the following formula (I): [Formula 19]

Represented by the formula (1) has at least 3 or more,  E is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;  s, t, and u each independently represent an integer of 0 to 3, and a plurality of E, X, Z, and Y may be the same or different. (In the above formula (I), R ¹ is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 3 carbon atoms. To 12 one-branched alkyl radicals, which are selected substituents;  Α is a hydrogen atom or a substituent selected from the group consisting of an aryloxy group, an atariloyloxy group, a glycidyloxy group and a chloromethyloxy group, and at least one of A is an aryloxy group, Atalyloyloxy, glycidyloxy, and chloromethyloxy groups which are selected substituents;  Ar is an aromatic hydrocarbon group having 6 to 12 carbon atoms;  Y is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, a substituted alkylene group having 1 to 12 carbon atoms, or a single bond;  Z represents a single bond or a substituent selected from the group consisting of O, —S, and —NH;  al is an integer from 1 to 9;  rl is an integer from 0 to 8;  al + rl≤9 n is 1. However,

A, Ar, al, rl may be the same or different Good. )]  The compound of the formula (1) is a compound represented by the following formula (4) to (6). 10. The resistive tie according to 9. [Formula 20]

(In the formulas (4) to (6), X and E are the same as described above.)  A resist compound represented by the following formula (2). [Formula 21]

[In the formula (2), X is the same as described above, a plurality of Xs may be the same or different, and G is the following formula (i to (V): [Formula 22]

Is a characteristic group derived from the structure of  X is bonded to three or more aromatic or aliphatic rings in formulas (i) to (V),  V represents an integer of 3 to 15. (In the above formulas (i) to (ii), R is a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and carbon R ³ is a hydrogen atom, a hydroxyl group, a non-cyclic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic carbon group having 3 to 12 carbon atoms. A hydrogen group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi): [Formula 23] 0 II H ₇ ( _V i - C- N one E ² - X, ^V1) Bruno (In the formula (vi), E ² is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms. ) Is a group strength which is also a selected group, r is an integer of 0 to 4, k is an integer of 1 to 7, and a plurality of R and r are each In the formulas (iv) to (v), E ′ may be the same or different and each independently represents a single bond, a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, Represents a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms or a substituted alkylene group having 1 to 12 carbon atoms, and X is bonded to E '. )}] 32. The resist conjugate according to claim 31, wherein the compound of the formula (2) is a compound represented by any one of the following formulas (9) to (14). [Formula 24]

(In the formula (9), X and R ² are the same as described above.) [Formula 25]

(In the formula (10), X is the same as described above.) [Formula 26]

(In the formula (11), X and k are the same as described above.) [Formula 27]

(In the formula (12), X is the same as described above.) [Formula 28]

(In the formula (14), X is the same as described above.)  A resist compound represented by the following formula (3), [Formula 30]

[In the formula (3), R ³ is a group consisting of a hydrogen atom, an acyclic hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, and a substituted alkyl group having 1 to 12 carbon atoms. X, E ² and k are the same as described above; B is the following formula (vi): [Formula 31] -NE ² -X ^(VV  ◦c = (In the formula (vi), X and E ² are the same as described above.) And E ¹ and E ¹ ′ may be the same or different and each independently represents a single bond or a divalent hydrocarbon group having 1 to 11 carbon atoms. However, the total number of carbon atoms of E ¹ and E ¹ is 0 to: L 1. J is a group selected from —O—, —S—, —NH— and a single bond. However, multiple B,

E ¹ ′, E ² , and J may be the same or different. ]  [34] The compound of claim 33, which is a compound represented by the following formula (8):  [Formula 32]

(In equation (8),

X, J and k are the same as described above, and a plurality of R ³ , E ² , X and J may be the same or different.  [35] A resist compound represented by the following formula (7):  [Formula 33]

(In the formula (7), E ² , X and k are the same as described above.) 36. The resist-bonded product according to claim 29, wherein X in each of the formulas (1) to (14) is represented by the following formula (II) or (III).  [Formula 34]

(In the formula (II) or (III), A is the same as described above, and m is an integer of 1 to 2.)