JP4815871B2 - Resist compound and resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resist composition which can be used for not only UV rays such as i-line and g-line but for visible rays, excimer laser light such as KrF, extreme UV rays (EUV), electron beams, X rays, and ion beams, to provide a resist compound to be used for the above composition, to provide a nonpolymer-based radiation-sensitive resist composition having high resolution, high heat resistance and solvent solubility in an easy preparation process, and to provide a resist compound to be used for the composition. <P>SOLUTION: The resist composition contains one or more kinds of resist compounds (A) satisfying all of the following conditions. The compound has (a) at least one crosslinking reactive group in the molecule, the group directly or indirectly inducing crosslinking reaction by irradiation with any radiation selected from a group consisting of visible rays, UV rays, excimer laser light, EUV rays, electron beams, X rays and ion beams; (b) one kind or more of functional groups selected from a group consisting of urea groups, urethane groups, amide groups and imide groups in the molecule; (c) 500 to 5,000 molecular weight; and (d) a branched structure. Resist compound satisfying the above conditions are presented. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a radiation-sensitive resist composition containing a resist compound represented by a specific chemical structural formula, which is useful as a non-polymer resist material, and a resist compound used therefor, and more particularly, to ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV). ), A radiation-sensitive material that is sensitive to radiation such as electron beams and X-rays. It is used for masks used in the manufacture of LSIs and VLSIs in the electronics field, and can produce high-resolution resist patterns with a high degree of integration. The present invention relates to a resist composition capable of producing a semiconductor element and a resist compound used therefor.

Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a resist thin film prepared by applying polymethyl methacrylate and a solution in which it is dissolved in a solvent for dissolving it onto a substrate is irradiated with ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), electron beams, X-rays, etc. As a result, a line pattern of about 0.1 μm is formed.
However, since the polymer resist has a large molecular weight of about 10,000 to 100,000 and the molecular weight distribution is wide, in lithography using the polymer resist, roughness is generated on the pattern surface in fine processing, and the pattern dimension is controlled. Becomes difficult and the yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce a finer pattern, various methods for reducing the molecular weight of a resist material have been disclosed.

  Examples of non-polymer resist materials are (1) positive and negative resists derived from fullerenes, (2) positive and negative resists derived from calixarene, and (3) starburst compounds. (4) a positive resist derived from a dendrimer, (5) a positive resist derived from a dendrimer / calixarene, and (6) a positive resist derived from a highly branched starburst compound. And (7) a positive resist derived from a starburst compound having an ester bond with trimesic acid as a central skeleton, (8) a negative resist derived from a cyclic polyphenol compound, and (9) derived from a polyphenol compound. Negative resists, and (10) calix resorcinarene It includes negative resists.

  About (1), although etching resistance is good, applicability | paintability and a sensitivity have not reached the practical use level (refer patent documents 1-5). About (2), although it is excellent in etching tolerance, since a solubility with respect to a developing solution is bad, a satisfactory pattern is not obtained (refer patent documents 6-8). Regarding (3), the image may be distorted during heat treatment after exposure because of low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and it cannot be said that it is practical (see Non-Patent Document 1). Regarding (5), the manufacturing process is complicated and the raw material is expensive, so it cannot be said that it is practical (see Patent Documents 12 and 13). About (6), since a manufacturing process is complicated and a raw material is expensive, it cannot be said that it is practical. Regarding (7), since the heat resistance is low, 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 Patent Document 14). About (8) and (9), amorphous property and etching resistance are not sufficient, and improvement is desired (see Patent Documents 15 to 17). Regarding (10), the amorphous nature and the safety solvent solubility are not sufficient, and improvement is desired (see Patent Documents 18 to 19).

JP-A-7-134413 JP 9-211182 A JP-A-10-282649 Japanese Patent Application Laid-Open No. 11-143074 Japanese Patent Laid-Open No. 11-258996 JP-A-11-72916 JP-A-11-322656 JP-A-9-236919 JP 2000-305270 A JP 2002-99088 A JP 2002-99089 A JP 2002-49152 A JP 2003-183227 A Japanese Patent Laid-Open No. 2002-328466 Japanese Patent Laid-Open No. 11-153863 JP 2003-207893 A JP 2004-334106 A JP-A-9-236919 JP 2004-18421 A Proceedings of SPIE vol. 3999 (2000) P1202-1206.

  The object of the present invention is not only ultraviolet rays such as i-line and g-line but also excimer laser light such as visible light, KrF, extreme ultraviolet (EUV), electron beam, X-ray, ion beam, etc. A radiation resist composition and a resist compound used therefor are provided. Still another object of the present invention is to provide a high-resolution, high heat-resistant and solvent-soluble non-polymeric radiation-sensitive resist composition and a resist compound used therefor by a simple production process.

As a result of intensive studies, the present inventors have found that a composition containing a compound that satisfies a specific condition is useful for solving the above problems.
That is, the present invention provides a resist composition containing one or more resist compounds (A) that satisfy all of the conditions (a) to (d).
(A) Crosslinking that causes a crosslinking reaction directly or indirectly by irradiation 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. Has at least one reactive group in the molecule.
(B) The molecule has one or more functional groups selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
(C) The molecular weight is 500-5000.
(D) It has a branched structure.
The present invention also provides a resist compound suitable for the resist compound (A).

  When the resist compound and the resist composition of the present invention are used, a high-resolution resist pattern can be produced, and a highly integrated semiconductor element can be produced.

Hereinafter, the present invention will be described in detail.
The resist composition of the present invention contains a resist compound (A). The resist compound (A) in the present invention satisfies all the following conditions (a) to (d) simultaneously.
(A) Crosslinking that causes a crosslinking reaction directly or indirectly by irradiation 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. Has at least one reactive group in the molecule.
Due to the cross-linking reactive group, the resist compound can selectively insolubilize the exposed portion and is used in a negative resist composition. Here, the crosslinking reaction means a chemical reaction in which a plurality of reaction points in the resist compound are linked by a covalent bond. The cross-linking reactive group has at least 1, preferably 2, more preferably 2 to 15 and particularly preferably 3 to 15 in the molecule. By setting it within such a range, it is possible to further improve the resolution and development performance.

Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenyl group, and a halogenated methyl group.
Among these, a carbon-carbon multiple bond group, an epoxy group, and a halogenated methyl group are preferable. Examples of the carbon-carbon multiple bond group include a vinyl group (CH ₂ ═CH—) and an allyl group (CH ₂ ═ _CH-CH 2 -), vinylene group-containing group ^(R 4 -CH = CH-), acryloyl group _{(CH 2 = CH-CO-)} , methacryloyl group _{(CH 2 = C (CH 3} ) -CO-), crotonoyl Group (CH ₃ —CH ₂ ═CH—CO—), fumaroyl group (trans type R ⁴ —OC—CH═CH—CO—), maleinoyl group (cis type R ⁴ —OC—CH═CH—CO—), etc. And carbon-carbon triple bonds such as propargyl group (CH≡C—) and acetylene group (R ⁴ —C≡C—). Of these, carbon-carbon double bonds such as vinyl group, allyl group, vinylene group, acryloyl group, and methacryloyl group, and carbon-carbon triple bonds such as propargyl group and acetylene group are more preferable. Vinyl group, allyl group , Acryloyl groups, methacryloyl groups, and propargyl groups are most preferred. The epoxy group include glycidyl group _{(CH 2 (-O-) CHCH 2} -) and the like. Examples of the halogenated methyl group include a chloromethyl group (ClCH ₂ —), a bromomethyl group (BrCH ₂ —), and a methyl iodide group (ICH ₂ —).
R ⁴ is a group selected from 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 one or more functional groups selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
The resist compound (A) is one or more functional groups selected from the group consisting of a urea group, an amide group, a urethane group, and an imide group, particularly one type selected from the group consisting of a urea group, an amide group, and a urethane group. It is preferable to include one or more of the above functional groups and three or more. Moreover, the functional group which has another nitrogen component may be included. Other functional groups include tertiary amine groups; quaternary ammonium groups; imino groups; azide groups; functional groups containing heterocyclic amines such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, morpholine, etc. For example, but not limited to. By having the functional group, heat resistance necessary for pattern production and substrate adhesion can be obtained, and resolution can be further improved. In addition, the process for producing a compound having a molecular weight of about 500 to 5000 can be simplified. In addition, it is preferable not to contain a basic functional group. If it has a basic functional group, the sensitivity may be lowered. Each branched molecular chain in the branched structure has at least one crosslinking reactive group, and each molecular chain has a urea bond, a urethane bond, an amide bond, and an imide bond (preferably a urea bond). It is preferable to have one or more selected from the group consisting of a bond and a urethane bond. By having the said structure, board | substrate adhesiveness can be improved and resolution can be improved further.

(C) The molecular weight is 500-5000.
The molecular weight is 500 to 5000, preferably 600 to 3000, and more preferably 700 to 2000. By making it in the above-mentioned range, it becomes possible to impart good film forming properties, and it is possible to further improve resolution and alkali development performance.

(D) It has a branched structure.
In the present invention, the “branched structure” refers to a structure satisfying at least one of the following (1) to (4).
(1) It has a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure.
(2) It has a quaternary carbon atom.
(3) It contains at least one aromatic ring or aliphatic ring having 3 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, it is possible to impart a stable amorphous property over a long period of time, and features such as excellent film forming properties, light transmittance, solvent solubility, and etching resistance necessary for pattern formation as a resist material Have Further, since the number of photosensitive groups can be increased, the sensitivity can be increased.

  In the present invention, the resist compound (A) preferably satisfies F ≦ 5 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)). When F is 5 or less, performance such as resolution and etching resistance does not deteriorate.

  The resist compound (A) in the present invention is preferably one represented by the following formula (1).

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

And at least 3 or more in formula (1),
E is a C1-C12 divalent acyclic hydrocarbon group, a C3-C12 divalent cyclic hydrocarbon group, or a C1-C12 substituted alkylene group;
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 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 to 3 carbon atoms. A substituent selected from the group consisting of 12 1-branched alkyl groups;
A is a hydrogen atom or a substituent selected from the group consisting of an allyloxy group, an acryloyloxy group, a glycidyloxy group, and a chloromethyloxy group, and at least one of A is an allyloxy group, an acryloyloxy group, a glycidyloxy group. A substituent selected from the group consisting of a group and a chloromethyloxy group;
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—;
a1 is an integer from 1 to 9;
r1 is an integer from 0 to 8;
a1 + r1 ≦ 9;
n is 1. However, the plurality of R ¹ , A, Ar, a1, and r1 may be the same or different. ]]

In formula (1) and formula (I),
Examples of the linear hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and hexyl. Group, octyl group, decyl group, dodecyl group, etc .;
Examples of the cyclic hydrocarbon group having 3 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclododecyl group;
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy. Group, hexyloxy group, octyloxy group, dodecyloxy group and the like;
Examples of the 1-branched alkyl group having 3 to 12 carbon atoms include isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 1-methylundecane group etc. can be mentioned;
Examples of the divalent acyclic hydrocarbon group having 1 to 12 carbon atoms include methylene group, ethylene group, propylene group, dimethylmethylene group, trimethylene group, tetramethylene group, t-butylene group, hexylene group, octylene group, A dodecylene group 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 aminomethylene group, hydroxylmethylene group, carboxylmethylene group, chloromethylene group, bromomethylene group, iodomethylene group, methoxymethylene group, ethoxymethylene group, propoxymethylene group, A butoxymethylene group, an acetylmethylene group, a cyanomethylene group, a nitromethylene group, etc .;
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.

  The compound of formula (1) is reacted with isocyanurate derived from diisocyanate, and aminophenols or hydroxyalkylphenols, and then, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray and It is produced by reacting a crosslinking reactive group introduction reagent that causes a crosslinking reaction by ion beam irradiation or a chemical reaction induced thereby. By using isocyanurate derived from diisocyanate, a branched polyphenol compound can be easily obtained.

  The method for producing the resist compound (A) used in the present invention is not particularly limited. In particular, after reacting a polyisocyanate having 3 or more isocyanate groups with aminophenols or hydroxyalkylphenols, visible light, ultraviolet light , Excimer laser, extreme ultraviolet (EUV), electron beam, X-ray and ion beam irradiation, or a cross-reactive group introduction reagent that causes a cross-linking reaction by a chemical reaction induced thereby reacts in the same way under a base catalyst. The container can be manufactured in all steps, which is preferable because it is simpler and more practical.

  The isocyanurate is not particularly limited, but tolylene diisocyanate, bis (isocyanatephenyl) methane, bis (isocyanatocyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane, metaxylene diisocyanate , Norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or isocyanurate derived from trimethylhexamethylene diisocyanate. Among them, isocyanurate derived from tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane, and metaxylene diisocyanate is preferred, tolylene diisocyanate, bis (isocyanatophenyl) methane, isophorone diisocyanate, And isocyanurates derived from bis (isocyanatomethyl) cyclohexane are particularly preferred.

The aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a functional group that has 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-amino Hydroquinone, 4-amino pyrogallol, 5-amino pyrogallol, 2-aminomethylphenol, 3-aminomethylphenol, 4-aminomethylphenol, 4-aminomethylcatechol, 3-aminomethylcatechol, 2-aminomethylresorcinol, 4- Aminomethyl resorcinol, 5-aminomethyl resorcinol, 2-aminomethyl hydroquinone, 4-aminomethyl pyrogallol, 5-aminomethyl pyrogallol, 2-aminophloroglicinol, 2-amino Such as chill phloroglucinol and the like. In particular, p-aminophenol and m-aminophenol are preferable.

  Examples of the hydroxyalkylphenols include 4-hydroxymethylphenol, 3-hydroxymethylphenol, 2-hydroxymethylphenol, 4-hydroxymethylcatechol, 3-hydroxymethylcatechol, 2-hydroxymethylresorcinol, 4-hydroxymethylresorcinol, 5 -Hydroxymethyl resorcinol, 2-hydroxymethyl hydroquinone, 4-hydroxymethyl pyrogallol, 5-hydroxymethyl pyrogallol, etc. are mentioned. In particular, 4-hydroxymethylphenol and 5-hydroxymethylresorcinol are preferable.

  The reaction between the isocyanurate, aminophenols or hydroxyalkylphenols, and a crosslinking reactive group introduction reagent is carried out by dissolving aminophenols or hydroxyalkylphenols in an aprotic polar solvent and then adding them to an aprotic polar solvent. Add dissolved isocyanurate or add aminophenols or hydroxyalkylphenols dissolved in aprotic polar solvent to isocyanurate dissolved in aprotic polar solvent, then stir for about 5 minutes to 24 hours And do it. When the compound having 3 or more isocyanate groups is liquid, it does not have to be dissolved in an aprotic solvent. In addition, it is preferable that it is dripped over about 1 to 150 minutes at the temperature of about -5 degreeC-100 degreeC. Thereby, an amino group or a hydroxyalkyl group selectively reacts with an isocyanate group. Although the reaction proceeds even without a catalyst, the reaction rate may be increased by using one or more base catalysts.

  Next, in order to introduce a crosslinking reactive group such as an acryloyl group in the same reaction vessel, a crosslinking reactive group introduction reagent such as acryloyl chloride is added in the presence of the base catalyst such as triethylamine at atmospheric pressure at room temperature. Let react for hours. After adding distilled water to the reaction solution to precipitate crystals, the resist compound (A) is obtained by washing with distilled water and / or purifying by column chromatography, high performance liquid chromatography, etc. and drying.

  The crosslinking reactive group introduction reagent referred to here means an acid having a crosslinking reactive group, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, an epihalohydrin, etc., for example, methacryloyl chloride. Acryloyl chloride, bromoethylene, bromopropene, 1-propenylphenyl chloride, chlorostyrene, bromochloromethane, 1-bromomethyl-4-chloromethylbenzene, especially acryloyl chloride, 3-bromopropene, epichlorohydrin, epibromohydride Phosphorus and bromochloromethane are preferred. Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group.

  As the aprotic polar solvent used in the above reaction, a compound having three or more isocyanate groups, aminophenols or hydroxyalkylphenols, a crosslinking reactive group introduction reagent, and a resist compound (A) as a product thereof can be dissolved. There is no particular limitation, and a conventionally known aprotic polar solvent can be used. Examples thereof include dimethylformamide and dimethylacetamide. These may be used alone or in combination of two or more.

  The base catalyst used in the above reaction may be an alkaline compound such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxy. It is preferable to use at least one of an alkaline compound such as TMAH or choline, or a metal compound such as an alkyl ammonium salt or alcoholate. Of these, trialkylamines such as triethylamine, triisopropylamine, and tributylamine are preferable, and triethylamine is particularly preferable.

  As other methods, after reacting the isocyanurate with aminophenols or hydroxyalkylphenols, the reaction solution is added to a large amount of water to crystallize, the filtered crystals are dissolved in acetone, In addition to a large amount of water, crystallization is performed to obtain an intermediate polyphenol compound. Thereafter, in the same or another container, in order to introduce a polyphenol compound and a crosslinking reactive group such as acryloyl group, a crosslinking reactive group introduction reagent such as acryloyl chloride is used at atmospheric pressure in the presence of the base catalyst such as triethylamine. The reaction is allowed to proceed for 2-4 hours at room temperature. After adding distilled water to the reaction solution to precipitate crystals, the resist compound (A) is obtained by washing with distilled water and / or purifying by column chromatography, high performance liquid chromatography, etc. and drying.

  In addition, after reacting the isocyanurate with aminophenols or hydroxyalkylphenols, the reaction solution is added to a large amount of water to crystallize, and the filtered crystals are dissolved in acetone, and again into a large amount of water. In addition, crystallization is performed to obtain an intermediate polyphenol compound. Then, in order to introduce a crosslinking reactive group such as an allyl group with a polyphenol compound in the same or another container, a crosslinking reactive group introduction reagent such as 3-bromopropene is present in a catalyst such as potassium carbonate or sodium iodide. The reaction is carried out at normal pressure and room temperature for 2 to 40 hours. After removing the salt from the reaction solution and concentrating the solvent, the resist compound (A) is obtained by washing with distilled water and / or purification by column chromatography, high performance liquid chromatography, and the like, and drying.

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

In 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 aminophenols or hydroxyalkylphenols, then, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam It is produced by reacting a cross-linking reactive group introducing agent that causes a cross-linking reaction by X-ray and ion beam irradiation or a chemical reaction induced thereby. By using isocyanurate derived from diisocyanate, a branched polyphenol compound having a branched structure can be easily obtained.
As the isocyanurate derived from diisocyanate, the above-mentioned compounds can be used.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.

  Reaction of isocyanurate derived from diisocyanate with aminophenols or hydroxyalkylphenols and cross-linking reactive group introduction reagents, compounds having three or more isocyanate groups, aminophenols or hydroxyalkylphenols and cross-linking reactivity The reaction can be carried out in the same manner as in the reaction with the group introduction reagent. After completion of the reaction, the corresponding compounds of the formulas (4) to (6) can be selectively obtained by separation by column chromatography or by using monomeric isocyanurate as a raw material. it can.

  Of the compounds represented by the formulas (4) to (6), compounds represented by the following formulas (19-1) to (23-4) are particularly preferable.

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

[In the formula (2), X is the same as described above, a plurality of X may be the same or different, and G represents the formulas (i) to (v):

And X is bonded to three or more aromatic rings or aliphatic rings in formulas (i) to (v). v represents an integer of 3 to 15.

{In the formulas (i) to (ii), R represents 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. A substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12; R ² is a hydrogen atom, a hydroxyl group, an acyclic hydrocarbon group having 1 to 12 carbon atoms, or a cyclic hydrocarbon having 3 to 12 carbon atoms Group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi):

(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. Either.)
A substituent selected from the group consisting of the following characteristic groups, r is an integer of 0 to 4, and k is an integer of 1 to 7. However, a plurality of R and r may be the same or different.

  In 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, or a divalent group having 3 to 12 carbon atoms. In the formula (2), X is bonded to E ′. }]

A linear hydrocarbon group having 1 to 12 carbon atoms of formula (2), a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, Examples of 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). .
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, List bromomethyl, nitromethyl, methoxyethyl, methylthioethyl, ethoxyethyl, ethylthioethyl, methoxyethoxyethyl, benzyloxyethyl, benzylthioethyl, chloroethyl, bromoethyl, nitroethyl, etc. Can do.

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

Monoisocyanate oligomers or triisocyanates are not particularly limited, but oligomers of isocyanate phenylmethane, tris (isocyanatephenyl) methane, tris (isocyanatephenyl) thiophosphate, mesitylene triisocyanate, triisocyanatebenzene, lysine ester triisocyanate, 1,6 , 11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, or bicycloheptane triisocyanate. Of these, oligomers of isocyanate phenylmethane, tris (isocyanatephenyl) methane, and tris (isocyanatephenyl) thiophosphate are particularly preferred.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.

  Reaction of oligomers or triisocyanates of monoisocyanates with aminophenols or hydroxyalkylphenols and crosslinkable reactive group introduction reagents, isocyanurates derived from the aforementioned diisocyanates, aminophenols or hydroxyalkylphenols and crosslinking reactivity The reaction can be carried out in the same manner as in the reaction with the group introduction reagent.

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

In the formulas (9) to (14), X, R ² and k are the same as described above.
The compound of the formula (9) is produced by reacting tris (isocyanatephenyl) methane, aminophenols, hydroxyalkylphenols and a crosslinking reactive group introduction reagent. By using tris (isocyanatophenyl) methane, a branched polyphenol compound can be easily obtained.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction of tris (isocyanatephenyl) methane with aminophenols or hydroxyalkylphenols is the same as the reaction of isocyanurates derived from the above-mentioned diisocyanates with aminophenols or hydroxyalkylphenols and cross-linking reactive group introduction reagents. It can be done by the method.

The compound of formula (10) is prepared by reacting tris (isocyanatophenyl) thiophosphate and aminophenols or hydroxyalkylphenols. By using tris (isocyanatephenyl) thiophosphate, a branched polyphenol compound can be easily obtained.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction between tris (isocyanatephenyl) thiophosphate and aminophenols or hydroxyalkylphenols can be carried out in the same manner as the reaction between the above-mentioned isocyanurates derived from diisocyanates and aminophenols or hydroxyalkylphenols. it can.

The compound of the formula (11) is produced by reacting an oligomer of isocyanate phenylmethane, an aminophenol or hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. A branched polyphenol compound can be easily obtained by using an oligomer of isocyanate phenylmethane.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction of an isocyanate phenylmethane oligomer with an aminophenol or hydroxyalkylphenol is the same as the reaction of an isocyanurate derived from the above-mentioned diisocyanate with an aminophenol or hydroxyalkylphenol and a crosslinking reactive group introduction agent. Can be done by the method.

The compound of the formula (12) is produced by reacting mesitylene triisocyanate, aminophenols or hydroxyalkylphenols and a crosslinking reactive group introduction reagent. By using mesitylene triisocyanate, a branched polyphenol compound can be easily obtained.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction of mesitylene triisocyanate with aminophenols or hydroxyalkylphenols can be carried out in the same manner as the reaction of isocyanurate derived from the aforementioned diisocyanates with aminophenols or hydroxyalkylphenols.

The compound of the formula (13) is produced by reacting triisocyanate benzene, aminophenols or hydroxyalkylphenols and a crosslinking reactive group introduction reagent. By using triisocyanate benzene, a branched polyphenol compound can be easily obtained.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction of triisocyanate benzene with aminophenols or hydroxyalkylphenols is carried out in the same manner as the reaction of isocyanurate derived from the above-mentioned diisocyanates with aminophenols or hydroxyalkylphenols and a crosslinking reactive group introduction reagent. It can be carried out.

The compound of the formula (14) is produced by reacting cyclohexane triisocyanate, aminophenols or hydroxyalkylphenols and a crosslinking reactive group introduction reagent. By using cyclohexane triisocyanate, a branched polyphenol compound can be easily obtained.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.
The reaction of cyclohexane triisocyanate with aminophenols or hydroxyalkylphenols is carried out in the same manner as the reaction of isocyanurate derived from the above-mentioned diisocyanates with aminophenols or hydroxyalkylphenols and crosslinking reactive group introduction reagents. It can be carried out.

  Of the compounds represented by the formulas (9) to (14), compounds represented by the following formulas (26-1) to (32-4) are particularly preferable.

  The resist compound (A) in the present invention is preferably one represented by the following formula (3).

[In the formula (3), R ³ is selected from the 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. The selected substituents, X, E ² and k are as defined above;
B is the formula (vi):

(In formula (vi), X and E ² are the same as 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 11. J is a substituent selected from the group consisting of —O—, —S—, —NH— and a single bond. However, a plurality of B, E ¹ , E ¹ ′, E ² , and J may be the same or different. ]

Examples of the acyclic hydrocarbon group having 1 to 12 carbon atoms, the cyclic hydrocarbon group having 3 to 12 carbon atoms, and the substituted alkyl group having 1 to 12 carbon atoms represented by R ^{3 in the} formula (3) include those represented by the formula (1) and The same can be illustrated.
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 in formulas (3) and (vi) The same thing as (1) can be illustrated. Examples of the divalent hydrocarbon group (E ¹ , E ¹ ′) having 1 to 11 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, decylene, undecylene and the like.

  The compound of the formula (3) is produced by reacting a burette body, an allohanate body, or a urethane body derived from diisocyanate, an aminophenol or a hydroxyalkylphenol, and a crosslinking reactive group introduction reagent. A branched polyphenol compound can be easily obtained by using a burette body, an allophanate body, or a urethane body derived from diisocyanate.

The burette, allophanate or urethane derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanatophenyl) methane, bis (isocyanatocyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene Of burette, allophanate or urethane derived from diisocyanate, bis (isocyanatemethyl) cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or trimethylhexamethylene diisocyanate either There it is preferable. Among these, a burette body derived from hexamethylene diisocyanate and a urethane body derived from tolylene diisocyanate are particularly preferable.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.

  The reaction between a burette body, an allophanate body or a urethane body derived from diisocyanate and an aminophenol or hydroxyalkylphenol is the isocyanurate derived from the diisocyanate, an aminophenol or hydroxyalkylphenol and a crosslinking reaction. The reaction can be carried out in the same manner as in the reaction with the sex group introduction reagent.

  Of the compounds represented by formula (3), those represented by formula (8) are preferred.

In formula (8), R ³ , E ² , X, J, k are the same as described above. However, the plurality of R ³ , E ² , X, and J 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 hydroxyalkylphenol and a crosslinking reactive group introduction reagent. By using a urethane body derived from diisocyanate, a branched polyphenol compound can be easily obtained.

Urethane derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanatephenyl) methane, bis (isocyanatocyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) cyclohexane , Metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or a urethane body derived from trimethylhexamethylene diisocyanate is preferable. Among these, a urethane body derived from tolylene diisocyanate is particularly preferable.
As the aminophenols or hydroxyalkylphenols, the aforementioned compounds can be used.

  The reaction between a urethane compound derived from diisocyanate and an aminophenol or hydroxyalkylphenol is a reaction of the above-mentioned isocyanurate derived from diisocyanate with an aminophenol or hydroxyalkylphenol and a crosslinking reactive group introduction agent. A similar method can be used.

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

  The resist compound (A) in the present invention is preferably one represented by the following formula (7).

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

  The compound of the formula (7) is produced by reacting a burette body derived from diisocyanate, aminophenols or hydroxyalkylphenols and a crosslinking reactive group introduction reagent. By using a burette body derived from diisocyanate, a branched polyphenol compound can be easily obtained.

The burette derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanatephenyl) methane, bis (isocyanatocyclohexyl) methane, phenylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanate methyl) It is preferably any of burettes derived from cyclohexane, metaxylene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, or trimethylhexamethylene diisocyanate. Of these, a burette derived from hexamethylene diisocyanate is particularly preferred.
The above compounds can be used as aminophenols or hydroxyalkylphenols.

  The reaction of the burette body derived from diisocyanate with aminophenols or hydroxyalkylphenol is the reaction of the above-mentioned isocyanurate derived from diisocyanate with aminophenol or hydroxyalkylphenol and a crosslinking reactive group introduction reagent. It can be performed in the same way.

  Of the compounds represented by the formula (7), compounds represented by the following formulas (25-1) to (25-4) are particularly preferable.

  The resist compound (A) in the present invention is preferably such that X in the formulas (1) to (14) is represented by the following formulas (II) to (III).

In 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 crosslinking reactive group introduction reagent. The compound in which X is represented by the formula (III) is produced by reacting a compound having 3 or more isocyanate groups and a hydroxyalkylphenol. By using a compound having 3 or more isocyanate groups, a branched polyphenol compound having a branched structure can be easily obtained.
As the compound having 3 or more isocyanate groups, the above compounds can be used.
Aminophenols or hydroxyalkylphenols are not particularly limited as long as they have a functional group that is higher in reactivity with isocyanate than phenolic hydroxyl groups.

  Examples of aminophenols used when X is a compound represented by the formula (II) include p-aminophenol, m-aminophenol, o-aminophenol, 4-aminocatechol, 3-aminocatechol, 2 -Aminoresorcinol, 4-aminoresorcinol, 5-aminoresorcinol, 2-aminohydroquinone, 4-aminopyrogallol, 5-aminopyrogallol, 2-aminophloroglicinol and the like. In particular, p-aminophenol and m-aminophenol are preferable.

Examples of hydroxyalkylphenols used when X is a compound represented by the formula (III) include 4-hydroxymethylphenol, 3-hydroxymethylphenol, 2-hydroxymethylphenol, 4-hydroxymethylcatechol, 3-hydroxymethylphenol, Hydroxymethyl catechol, 2-hydroxymethyl resorcinol, 4-hydroxymethyl resorcinol, 5-hydroxymethyl resorcinol, 2-hydroxymethyl hydroquinone, 4-hydroxymethyl pyrogallol, 5-hydroxymethyl pyrogallol and the like. In particular, 4-hydroxymethylphenol and 5-hydroxymethylresorcinol are preferable.
The reaction of a compound having three or more isocyanate groups with aminophenols or hydroxyalkylphenols can be carried out by the method described above.

  The nitrogen content of the resist compound (A) is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and particularly preferably 5 to 15% by mass. When the nitrogen element content is in the above range, the sensitivity and resolution are excellent, and heat resistance and substrate adhesion necessary for pattern production can be obtained.

  The resist compound (A) has 3 or more amino groups, a compound obtained by reacting hydroxybenzoic acid, dihydroxybenzoic acid, or trihydroxybenzoic acid with a crosslinking reactive group introduction reagent in the presence of a base catalyst. It can also be obtained by condensing the compound. This method is preferable because by-products can be suppressed.

  The compound having 3 or more amino groups is not particularly limited, but mesitylenetriamine, triaminobenzene, pararoseaniline, tris (aminophenylmethane), tris (aminophenyl) thiophosphate, lysine ester triamine, 1,6, Examples include 11-undecanetriamine, 1,8-diamino-4-aminomethyloctane, 1,3,6-hexamethylenetriamine, bicycloheptanetriamine, norbornanetriamine and the like. Among these compounds, mesitylenetriamine, triaminobenzene, and pararose aniline are particularly preferable.

The resist compound (A) is obtained by condensing a compound obtained by reacting aminophenols or hydroxyalkylphenols with a crosslinking reactive group introduction reagent in the presence of a base catalyst and a compound having 3 or more carboxyl groups. Can also be obtained. This method is preferable because by-products can be suppressed.
Examples of the compound having 3 or more carboxyl groups include benzenetetracarboxylic acid, cyclohexanetetracarboxylic acid, benzenetricarboxylic acid, cyclohexanetricarboxylic acid, and the like. Particularly, benzenetricarboxylic acid such as trimesic acid and cyclohexanetricarboxylic acid such as each hydrogenated trimesic acid. Acid is preferred.

  The resist composition of the present invention contains one or more resist compounds (A) described above. When one type of resist compound (A) is used, high resolution is obtained, and when two or more types are used, film formability and substrate adhesion may be improved.

  The resist composition of the present invention is directly or indirectly 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. It is desirable to add a compound (B) that generates radicals or cations.

Among the compounds (B), as a compound (B-1) that generates radicals, a compound that generates radicals by interacting with a radical initiator, a photoexcited sensitizer, and mainly sensitized by ultraviolet light. A compound having both a sensation and a radical generating ability due to this is mentioned. Examples of the radical initiator include peroxides such as benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; azobisisobutyronitrile, azobis Azo compounds such as cyclohexanenitrile and phenylazotriphenylmethane; persulfates such as potassium persulfate and ammonium persulfate; organoaluminum compounds such as triethylaluminum, trimethylaluminum, ethylaluminum dichloride, diethylaluminum chloride; tetraethyllead, diethylzinc , Diethylcadmium, Tetraethyltin and other organometallic compounds; titanium tetrachloride, titanium trichloride, aluminum chloride, aluminum bromide, stannic chloride, zinc chloride, boron trifluoride, trifluoride C containing diethyl etherate include chlorides such as phosphorus pentafluoride. Examples of the compounds that generate radicals by interacting with a photoexcited sensitizer in various ways include various titanocenes described in, for example, JP-A Nos. 59-152396 and 61-151197 ( Specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5, 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4,6-trifluorophen-1-yl, dicyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, -Di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- Bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl, etc.), Bull. Chem. Soc. Japan. 33,565 (1960) and J.A. Org. Chem. 36 [16] 2262 (1971) and hexaarylbiimidazoles (specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5, 5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) biimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'- Tetra (p-chlorophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-chloro-p-methoxyphenyl) biimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ' 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o, p-dichlorophenyl) -4, 4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazoles and the like, hexaarylbiimidazoles having a halogen substituent on the benzene ring), halogenated hydrocarbon derivatives, diaryliodonium salts, organic peroxides, and the like. An oxide etc. are mentioned. Examples of the compound having both a sensitization effect mainly by ultraviolet light and a radical generating ability thereby include, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-isopropoxy-1,2-diphenyl Ethan-1-one, (1′-hydroxycyclohexyl) phenyl ketone, 2-methyl-1- (4′-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- (N, N -Dimethylamino) -1- (4'-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1- [4 ′-(2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one Conductors, benzoic acid esters such as 4- (N, N-dimethylamino) benzoic acid isoamyl ester, 4- (N, N-dimethylamino) benzoic acid ethyl ester, (η ⁵ -2,4-cyclopentadiene-1 -Yl) [(1,2,3,4,5,6-η)-(1-isopropylbenzene) -organometallic compounds such as iron hexafluorophosphate, heteroaromatic rings such as 2,4-diethylthioxanthone A compound etc. can be illustrated.

  Among the compounds (B), examples of the compound (B-2) that generates a cation include at least one selected from the group consisting of compounds represented by the following formulas (33) to (40).

In formula (33), R ²³ may be the same or different and each independently represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or carbon. 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 a halogen atom. Yes, X ^- represents 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 sulfonic acids having a halogen-substituted aryl group having 6 to 12 carbon atoms An ion or a halide ion.

  The compound represented by the formula (33) is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate. Diphenyl-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4- Hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenyl Rufonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4 -Fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenyl Sulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylpheny Sulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoro At least one selected from the group consisting of lomethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium-10-camphorsulfonate, and diphenyl-4-hydroxyphenylsulfonium-10-camphorsulfonate It is preferable.

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

  The compound represented by the formula (34) is bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butyl). Phenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) iodonium- 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4- t-butyl Enyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium-10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium-10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluoro Benzenesulfonate, diphenyliodoni Muhexafluorobenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium per Fluoro-n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, and bis (4-trifluoromethylphenyl) iodonium-10-camphor It is preferably at least one selected from the group consisting of sulfonates.

In 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—, where R ′ is carbon. 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 6 to 12 carbon atoms. A halogen-substituted aryl group.

  The compound represented by the formula (35) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxiimi N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthyl Imide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N -(Perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene It is preferably at least one selected from the group consisting of -2,3-dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide.

In formula (36), R ²⁶ may be the same or different, and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a group having 3 to 12 carbon atoms. A cyclic alkyl group, 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 hydroxyl group, a halogen, or a haloalkyl group having 1 to 12 carbon atoms.

  The compound represented by the formula (36) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It should be at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone, and di (4-tolufluoromethylphenyl) disulfone. Is preferred.

In the formula (37), R ²⁷ may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a group having 3 to 12 carbon atoms. A cyclic alkyl group, 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, or an alkoxyl group having 1 to 12 carbon atoms.

  The compound represented by the formula (37) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile, and It is preferably at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (38), R ²⁸ may be the same or different, and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.
The compound represented by the formula (38) is selected from the group consisting of monochloroisocyanuric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dibromoisocyanuric acid, trichloroisocyanuric acid, and tribromoisocyanuric acid It is preferable that there is at least one kind.

In formulas (39) and (40), R ²⁹ and R ³⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group; a cyclopentyl group or a cyclohexyl group. A cycloalkyl group having 3 to 12 carbon atoms such as alkenyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group and propoxy group; aryl group such as phenyl group, toluyl group and naphthyl group, preferably , An aryl group having 6 to 10 carbon atoms. L ²⁹ and L ³⁰ 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-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ 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):

In represented by ^{substituents, -R a -C (= O)} -R b -, - R a -C (= O) -O-R b -, - R a -C (= O) -NH-R b -, or ^-R c ^{-O-R d} - (where, ^{R a} and ^{R b} may be the same or different, each independently represent a single bond or an alkylene group having 1 to 3 carbon atoms, and ^{R a} the total number of carbon atoms of R ^b is an 0 to 3; R ^c and R ^d may be the same or different, each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, R ^c and R ^{d 29} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X ²⁹ and X ^30. Are the following formulas (42):

(In formula (42), Z <^32> is respectively independently a C1-C3 alkyl group, a C3-C10 cycloalkyl group, or a C6-C10 aryl group, R <^32>. Is an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 3).
It is group shown by these.

  As other compounds (B), bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutyl) Bissulfonyldiazomethanes such as sulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) ) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3 , 5-Triazine, To Scan (2,3-dibromopropyl) a halogen-containing triazine derivatives such as isocyanurate.

  Moreover, the said (B) component can be used individually or in mixture of 2 or more types. In the composition of the present invention, the amount of component (B) used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, still more preferably 1 to 15 parts per 100 parts by weight of the resist compound. Parts by weight. The above range is preferable because the sensitivity, resolution, and cross-sectional shape of the resist pattern are good.

  The resist composition of the present invention includes, as necessary, other components (C), a crosslinking agent, a dissolution accelerator, a dissolution control agent, a sensitizer, and a surface activity, as long as the object of the present invention is not impaired. One or more kinds of various additives such as an agent can be added.

[1] Crosslinking agent In the present invention, in order to increase sensitivity, a carbon-carbon multiple bond group, cyclopropyl group, azide group, resin vinyl group, allyl group, cinnamoyl group, vinylsilyl group, epoxy group, halogenated methyl group, A compound having a halogenated phenyl group or a resin can also be added, in particular, a compound having 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 a resin is preferable.
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, and particularly preferably 5 parts by weight or less per 100 parts by weight of the resist compound.

[2] Sensitizer The sensitizer has an action of absorbing energy of irradiated radiation and transmitting the energy to the compound (B), thereby increasing the amount of radicals or cations generated, It is a component that improves the apparent sensitivity of the resist. Examples of such a sensitizer include triphenylmethane leuco dyes such as leuco crystal violet and leucomalachite green, erythrosin and eosin Y disclosed in US Pat. No. 3,479,185. Photoreducible dyes, Michler's ketone, aminostyryl ketone, aromatics such as benzophenone and biacetyl disclosed in US Pat. No. 3,549,367, US Pat. No. 3,652,275, etc. Ketones, β-diketones shown in U.S. Pat. No. 3,844,790, indanones found in U.S. Pat. No. 4,162,162, shown in JP-A-52-112681 Ketocoumarins, aminostyrene derivatives and aminophenols disclosed in JP-A-59-56403. Butadiene derivatives, aminophenyl heterocycles found in US Pat. No. 4,594,310, julolidine heterocycles shown in US Pat. No. 4,966,830, JP-A-5-241338 The pyromethene dyes, pyrenes, phenothiazines, fluorenes and the like shown in the above can be mentioned, but are not particularly limited.
These sensitizers can be used alone or in combination of two or more. The blending 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 compound.

[3] Surfactant The surfactant is a component having an action of improving the coating property and striation of the resist composition of the present invention, the developability as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, preferred surfactants are nonionic surfactants. Nonionic surfactants have better affinity with the solvent used in the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Pepol (Toho Chemical Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.) Each series such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) can be mentioned, but is not particularly limited.
The blending amount of the surfactant is preferably 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of the resist compound.

[4] Other additives other than the above-mentioned crosslinking agent, sensitizer, and surfactant Further, the resist composition of the present invention contains the above-mentioned crosslinking agent as necessary, as long as the object of the present invention is not impaired. , Sensitizers, and other additives other than surfactants can be added alone or in combination. Examples of other additives include a dissolution accelerator, a dissolution control agent, a dye, a pigment, and an adhesion assistant. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.
The resist composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, as necessary. 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.

  Examples of the solvent used for preparing the resist composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether Acetate, propylene glycol mono-n-butyl ether acetate, etc. Pyrene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; lactic acid such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and n-amyl lactate Esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Other esters such as cetate, 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 and N-methylpyrrolidone; γ- Although lactones, such as lactone, can be mentioned, it does not specifically limit. These solvents can be used alone or in combination of two or more.

  The resist composition of the present invention is irradiated with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray and ion beam or chemical reaction induced thereby, as long as the object of the present invention is not impaired. A compound and / or resin having a vinyl group, an allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a chloromethyl group, and a halogenated phenyl group, which are crosslinking reactive groups that cause a crosslinking reaction, can be used in combination. The compound and / or resin having a crosslinking reactive group is not particularly limited, but the compound and / or resin soluble in the alkaline aqueous solution, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam. A compound and / or a polymer produced by reacting a crosslinking reactive group introduction reagent that undergoes a crosslinking reaction by X-ray and ion beam irradiation or a chemical reaction induced thereby in the presence of a base catalyst, or a derivative thereof Can be mentioned. The term “crosslinking reactive group introduction reagent” as used herein refers to an acid having a crosslinking reactive group, an acid chloride, an acid anhydride, a carboxylic acid derivative compound such as dicarbonate, an alkyl halide, or the like. Of these, acid chlorides are particularly preferred. The crosslinking reactive group is a vinyl group, an allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a halogenated methyl group, or a halogenated phenyl group. One or more of these may be mixed and used.

  The composition of the resist composition of the present invention is usually 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) 0 in the total solid content. 0.001 to 50 weight is preferable, and 90 to 99.999 wt% of the resist compound (A) and 0.001 to 10 weight of the compound (B) are more preferable in the total solid content. By setting it within the above range, the performance such as resolution is excellent. In the case where it functions as a negative resist without the compound (B) in the total solid content, 100% by weight of the resist compound (A) is particularly preferable.

  In the present invention, the resist substrate is a resist substrate in which a resist film made of the resist composition is formed on the substrate, and the pattern formation substrate is obtained by exposing and developing the resist film on the resist substrate. A substrate having a patterned resist film. The “pattern forming material” is a composition formed on a resist substrate and capable of forming a pattern by irradiation with light, extreme ultraviolet (EUV), electron beam or radiation, etc., and is synonymous with “resist film”. . A “pattern wiring substrate” is a substrate having a patterned wiring obtained by etching a pattern forming substrate.

  As a method for forming a resist pattern using the resist composition of the present invention, a step of coating the resist composition on a substrate to form a resist film, a step of heat-treating the resist film as necessary, and a resist film visible After irradiating with radiation selected from the group consisting of light rays, ultraviolet rays, excimer lasers, extreme ultraviolet rays (EUV), electron beams, X-rays, and ion beams, and if necessary after heat treatment And a step of developing the exposed resist film using an alkali developer.

  In order to form a resist pattern, first, the resist composition of the present invention is applied to a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, cast coating, roll coating or the like. A resist film is formed. If necessary, a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance.

  Next, the coated substrate is heated as necessary. The heating condition varies depending on the composition of the radiation-sensitive composition, but is preferably 20 to 250 ° C, more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern 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. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating condition varies depending on the composition of the radiation-sensitive composition, but is preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

  Next, the exposed resist film is developed with a resist soluble developer to form a predetermined resist pattern. As the resist-soluble developer, the same solvent as the resist solution can be used. For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono -Ethylene glycol monoalkyl ether acetates such as n-butyl ether acetate; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Propylene glycol monoalkyl ether acetates; methyl lactate, ethyl lactate (EL), lactic acid Lactate esters such as propyl, lactate n-butyl and lactate n-amyl; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, propionic acid Aliphatic carboxylic acid esters such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; 2- Ketones such as butanone, 3-heptanone, 4-heptanone and cyclohexanone; Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-lactone There is no particular limitation, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

Further, an appropriate amount of the surfactant can be added to the resist-soluble developer. This is preferable since the wettability of the developer with respect to the resist can be improved.
After forming the resist pattern, the pattern wiring board is obtained by etching. The etching method can be performed by a known method such as dry etching using a plasma gas.
Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

The resist pattern can be peeled off 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. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
The wiring board obtained by using the resist composition of the present invention can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the embodiment 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. The analysis results are shown in Tables 1 and 2. In Table 1, the number of atoms of each compound is shown as a value of the sexual expression, the value of the weight percentage of the element is shown as a calculated value and an actual measurement value, and F = total number of atoms / (total number of carbon atoms−total oxygen The value obtained by calculating the value of (number of atoms). ^{The 1} H-NMR measurement results are shown in Table 2.

Synthesis Example 1: Synthesis of Compound (26-1) A 27 wt% solution of triphenylmethane triisocyanate (TPMTI) in ethyl acetate / monochlorobenzene (70/3 (weight ratio)) (Bayer Desmodur RE, NCO equivalent: 441) , Nonvolatile content: 27% by weight) A solution obtained by adding 3 ml of dimethimecetamide (DMAc) to 2.21 g was added using a dropping funnel, and 0.5 ml of p-aminophenol (AP) in 5 ml of DMAc (1.0 equivalent). The solution was slowly added dropwise and stirred at room temperature for 1 hour. Furthermore, 2.12 g (22.5 mmol) of acryloyl chloride (ACROS reagent) and 2.29 g of triethylamine (Kanto Chemical Co., Ltd. reagent) were slowly added dropwise and stirred at room temperature for 3 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, white powder was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate / DMAc = 3/4/100 (volume ratio), and the main component was taken out. Finally, vacuum drying was performed to obtain 0.89 g of Compound (26-1).

Synthesis Example 2 Synthesis of Compound (26-2) A solution obtained by adding 3 ml of DMAc to 2.21 g of a 27 wt% solution of TPMTI in ethyl acetate / monochlorobenzene (70/3 (weight ratio)) was added using a dropping funnel. The solution was slowly added dropwise to a solution of 55 g / 5 mmol (1.0 equivalent) of DMAc in 5 ml and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the crystal separated by filtration was dissolved in acetone, and then added 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 / ethyl acetate / DMAc = 3/4/100 (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 (Kanto Chemical Co., Ltd.), sodium iodide (Kanto Chemical) (Reagents manufactured by Co., Ltd.) 0.036 g (0.25 mmol) and 30 ml of acetone were added, followed by stirring at 55 ° C. for 24 hours in a nitrogen stream. After completion of the reaction, the salt was filtered and the solvent was concentrated, and then purified by column chromatography using a mixed solvent of hexane / ethyl acetate / DMAc = 3/4/100 (volume ratio) to take out the main component. Finally, vacuum drying was performed to obtain 0.86 g of compound (26-2).

Synthesis Example 3 Synthesis of Compound (26-3) A solution obtained by adding 3 ml of DMAc to 2.21 g of a 27 wt% solution of TPMTI in ethyl acetate / monochlorobenzene (70/3 (weight ratio)) was added using a dropping funnel. The solution was slowly added dropwise to a solution of 55 g / 5 mmol (1.0 equivalent) of DMAc in 5 ml and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the crystal separated by filtration was dissolved in acetone, and then added 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 / ethyl acetate / DMAc = 3/4/100 (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 added, and the mixture was heated to 40 ° C. and dissolved uniformly, and then 48.5 wt% sodium hydroxide. 0.32 g of an aqueous solution was added dropwise over 90 minutes. During this period, the temperature was gradually raised, and after completion of the dropping, the system was brought to 65 ° C. and stirred for 30 minutes. Then, excess epichlorohydrin and 2-propanol are distilled off from the product under reduced pressure, dissolved in 2 g of methyl isobutyl ketone, 0.02 g of 48.5 wt% sodium hydroxide aqueous solution is added, and the mixture is stirred at 65 ° C. for 1 hour. did. Thereafter, an aqueous sodium phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Subsequently, methyl isobutyl ketone was completely removed, and finally, drying under reduced pressure was performed to obtain 0.22 g of compound (26-3).

Synthesis Example 4: Synthesis of Compound (26-4) A solution obtained by adding 3 ml of DMAc to 2.21 g of a 27 wt% solution of TPMTI in ethyl acetate / monochlorobenzene (70/3 (weight ratio)) was added using a dropping funnel. The solution was slowly added dropwise to a solution of 55 g / 5 mmol (1.0 equivalent) of DMAc in 5 ml and stirred at room temperature for 1 hour. Further, 3.24 g (25 mmol) of bromochloromethane and 2.29 g of triethylamine (a reagent manufactured by Kanto Chemical Co., Inc.) were slowly added dropwise at room temperature. For 3 hours. When the reaction solution was added to a large amount of water and reprecipitation was repeated, white powder was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate / DMAc = 3/4/100 (volume ratio), and the main component was taken out. Finally, vacuum drying was performed to obtain 0.67 g of compound (26-4).

Synthesis Example 5: Synthesis of Compound (27-1) 2.21 g of a 27 wt% solution of TPMTI in ethyl acetate / monochlorobenzene (70/3 (weight ratio)) and 3,0-dihydroxybenzyl alcohol (DHBA) 0.70 g / A reaction of 5 mmol (1.0 equivalent) and 4.24 g (45.0 mmol) of acryloyl chloride was reacted in the same manner as in Synthesis Example 1 to obtain 1.02 g of compound (27-1).

Synthesis Example 6 Synthesis of Compound (27-2) 2.21 g of TPMTI in 27% by weight of ethyl acetate / monochlorobenzene (70/3 (weight ratio)), 0.70 g / 5 mmol (1.0 equivalent) of DHBA, and 3 -Reaction of 6.04 g (50 mmol) of bromopropene was carried out in the same manner as in Synthesis Example 2 to obtain 0.99 g of compound (27-2).

Synthesis Example 7 Synthesis of Compound (27-3) 2.21 g of TPMTI in 27% by weight of ethyl acetate / monochlorobenzene (70/3 (weight ratio)), 0.70 g / 5 mmol (1.0 equivalent) of DHBA, and epichlorohydrin 7.2 g (185.0 mmol) of the reaction was reacted in the same manner as in Synthesis Example 3 to obtain 0.55 g of compound (27-3).

Synthesis Example 8 Synthesis of Compound (27-4) 2.21 g of a 27 wt% solution of TPMTI in ethyl acetate / monochlorobenzene (70/3 (weight ratio)), 0.70 g / 5 mmol (1.0 equivalent) of DHBA, and bromo The reaction of 6.48 g (50 mmol) of chloromethane was reacted in the same manner as in Synthesis Example 4 to obtain 0.67 g of compound (27-4).

Synthesis Example 9: Synthesis of Compound (28-1) 27% by weight solution of Tris (phenylisocyanate) thiophosphate (TIPTP) in ethyl acetate / chlorobenzene (70/3 (weight ratio)) (Death module RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content: 27 wt%) 2.91 g of AP, 0.55 g / 5 mmol (1.0 equivalent) of AP, and 2.12 g (22.5 mmol) of acryloyl chloride were reacted in the same manner as in Synthesis Example 1 to obtain a compound ( 28-1) 0.62 g was obtained.

Synthesis Example 10: Synthesis of Compound (28-2) 27 wt% TIPTP in ethyl acetate / chlorobenzene (70/3 (weight ratio)) (Desmodur RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content: 27 wt%) The reaction of 2.91 g, AP 0.55 g / 5 mmol (1.0 equivalent), and 3-bromopropene 3.02 g (25 mmol) was reacted in the same manner as in Synthesis Example 2 to obtain 0.65 g of compound (28-2). It was.

Synthesis Example 11 Synthesis of Compound (28-3) TIPTP in ethyl acetate / chlorobenzene (70/3 (weight ratio)) 27% by weight solution (Desmodur RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content: 27% by weight) The reaction of 2.91 g, AP 0.55 g / 5 mmol (1.0 equivalent), and epichlorohydrin 1.8 g (92.5 mmol) was reacted 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) 27% by weight solution of TIPTP in ethyl acetate / chlorobenzene (70/3 (weight ratio)) (Desmodur RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content: 27% by weight) The reaction of 2.91 g, 0.55 g / 5 mmol (1.0 equivalent) of AP, and 3.24 g (25 mmol) of bromochloromethane was performed in the same manner as in Synthesis Example 4 to obtain 0.61 g of compound (28-4). .

Synthesis Example 13: Synthesis of Compound (29-1) Polymethylene polyisocyanate (MDI) (Sumidur 44V20 manufactured by Sumika Bayer Urethane Co., Ltd., NCO equivalent: 135, nonvolatile content: 100% by weight) 0.62 g was charged with 5 ml of DMAc. Using the dropping funnel, the added solution was reacted with 0.55 g / 5 mmol (1.0 equivalent) of AP and 2.12 g (22.5 mmol) of acryloyl chloride in the same manner as in Synthesis Example 1, and compound (29-1 ) 0.55 g was obtained.

Synthesis Example 14: Synthesis of Compound (29-2) 0.62 g of MDI (Sumika Bayer Urethane Co., Ltd. Sumidur 44V20, NCO equivalent: 135, nonvolatile content: 100% by weight) and AP 0.55 g / 5 mmol (1. 0 equivalents) and 3.02 g (25 mmol) of 3-bromopropene were reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (29-2).

Synthesis Example 15: Synthesis of Compound (29-3) 0.62 g of MDI (Sumika Bayer Urethane Co., Ltd. Sumidur 44V20, NCO equivalent: 135, nonvolatile content: 100% by weight) and 0.55 g / 5 mmol of AP (1. 0 equivalents) 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 (29-3).

Synthesis example 16: Synthesis | combination of compound (29-4) 0.62g and 0.55-g / 5 mmol of AP (Mid (Sumika Bayer Urethane Co., Ltd. product Sumidur 44V20, NCO equivalent: 135, non-volatile matter: 100 weight%) 0 equivalents) 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 (29-4).

Synthesis Example 17: Synthesis of Compound (24-1) 75 wt% ethyl acetate solution of trimethylolpropane adduct (TDITMP) of tolylene diisocyanate (Sumidur L75 manufactured by Sumika Bayer Urethane Co., Ltd., NCO equivalent: 324, non-volatile (Min: 75 wt%) 1.58 g, AP 0.55 g / 5 mmol (1.0 equivalent), and acryloyl chloride 2.12 g (22.5 mmol) were reacted in the same manner as in Synthesis Example 1 to obtain compound (24- 1) 0.58 g was obtained.

Synthesis Example 18 Synthesis of Compound (24-2) 1.58 g of 75% by weight ethyl acetate in TDITMP (Sumidur L75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 324, nonvolatile content: 75% by weight), The reaction of AP 0.55 g / 5 mmol (1.0 equivalent) and 3-bromopropene 3.02 g (25 mmol) was reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (24-2).

Synthesis Example 19: Synthesis of Compound (24-3) 1.58 g of TDITMP in 75 wt% ethyl acetate (Sumidur L75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 324, nonvolatile content: 75 wt%), AP 0.55 g / 5 mmol (1.0 equivalent) and epichlorohydrin 1.8 g (92.5 mmol) were reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (24-3).

Synthesis Example 20 Synthesis of Compound (24-4) 1.58 g of TDITMP in 75% by weight ethyl acetate (Sumidur L75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 324, nonvolatile content: 75% by weight), A reaction of AP 0.55 g / 5 mmol (1.0 equivalent) and bromochloromethane 3.24 g (25 mmol) was reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (24-4).

Synthesis Example 21: Synthesis of Compound (25-1) Hexamethylene diisocyanate burette body (HDI) methoxypropyl acetate / xylene 75 wt% solution (Sumidule N75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 255, Nonvolatile content: 75 wt%) 1.31 g, AP 0.55 g / 5 mmol (1.0 equivalent), and acryloyl chloride 2.12 g (22.5 mmol) were reacted in the same manner as in Synthesis Example 1 to obtain compound (25 -1) 0.58 g was obtained.

Synthesis Example 22: Synthesis of Compound (25-2) HDI in methoxypropyl acetate / xylene 75 wt% solution (Sumidule N75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 255, nonvolatile content: 75 wt%) The reaction of 31 g, AP 0.55 g / 5 mmol (1.0 equivalent), and 3-bromopropene 3.02 g (25 mmol) was carried out in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (25-2). .

Synthesis Example 23: Synthesis of Compound (25-3) HDI in methoxypropyl acetate / xylene 75 wt% solution (Sumijoule N75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 255, nonvolatile content: 75 wt%) The reaction of 31 g, AP 0.55 g / 5 mmol (1.0 equivalent), and epichlorohydrin 1.8 g (92.5 mmol) was reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (25-3).

Synthesis Example 24 Synthesis of Compound (25-4) HDI in methoxypropyl acetate / xylene 75 wt% solution (Sumidule N75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 255, nonvolatile content: 75 wt%) The reaction of 31 g, AP 0.55 g / 5 mmol (1.0 equivalent), and bromochloromethane 3.24 g (25 mmol) was reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (25-4).

Synthesis Example 25 Synthesis of Compound (19-1) Tolylene diisocyanate isocyanurate (TDI) in 50% by weight butyl acetate (Dainippon Ink Industries Barnock D-800, NCO equivalent: 592, nonvolatile content: 51% by weight ) 2.89 g, 0.55 g (1.0 equivalent) of AP, and 2.12 g (22.5 mmol) of acryloyl chloride were reacted in the same manner as in Synthesis Example 1 to obtain 0.58 g of compound (19-1). Got.

Synthesis Example 26: Synthesis of Compound (19-2) 2.89 g of a TDI butyl acetate solution (Bernock D-800 manufactured by Dainippon Ink Industries, Ltd., NCO equivalent: 592, nonvolatile content: 51 wt%), AP0. The reaction of 55 g / 5 mmol (1.0 equivalent) and 3-bromopropene 3.02 g (25 mmol) was reacted in the same manner as in Synthesis Example 2 to obtain 0.34 g of compound (19-2).

Synthesis Example 27: Synthesis of Compound (19-3) 2.89 g of TDI in 50% by weight of butyl acetate (Dainippon Ink Industries Vernock D-800, NCO equivalent: 592, nonvolatile content: 51% by weight), AP0. A reaction of 55 g / 5 mmol (1.0 equivalent) and 1.8 g (92.5 mmol) of epichlorohydrin was reacted in the same manner as in Synthesis Example 3 to obtain 0.65 g of compound (19-3).

Synthesis Example 28: Synthesis of Compound (19-4) 2.89 g of a TDI butyl acetate solution (Bernock D-800 manufactured by Dainippon Ink Industries, Ltd., NCO equivalent: 592, nonvolatile content: 51 wt%), AP0. The reaction of 55 g / 5 mmol (1.0 equivalent) and 3.24 g (25 mmol) of bromochloromethane was reacted in the same manner as in Synthesis Example 4 to obtain 0.58 g of compound (19-4).

Examples 1-36, Comparative Example 1
The resist compound (A), compound (B) and solvent described in Table 3 were made into a uniform solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm 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 formability of the obtained resist films.

  After spin-coating a resist on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven to form a resist film having a thickness of 0.2 μm. In Examples 1 to 32, the resist film was exposed to i-line having a wavelength of 365 nm, and Examples 33 to 36 and Comparative Example 1 were exposed to an electron beam, and then post-exposure baked in an oven (No. 1). Table 4). Development was performed with DMAc for 5 seconds at 23 ° C. by a static method. Thereafter, it was dried to form a negative resist pattern. Each obtained resist pattern was evaluated by the following method. The evaluation results are shown in Table 5.

(1) Compound Safety Solvent Solubility Test A solubility test of the resist compound (A) in a safe solvent was performed at 23 ° C. The amount dissolved in the solvent most selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethyl lactate was evaluated according to the following criteria.
A: dissolved 5% by weight or more B: dissolved 0.1% by weight or more to less than 5% by weight C: not dissolved (2) Evaluation of film formability of resist film A resist composition was formed on a silicon wafer with a spin coater The resist film was formed by spin coating, and then heated on a hot plate at 110 ° C. for 60 minutes, and the resist film on the 6-inch silicon wafer was evaluated according to the following criteria.
A: Good surface property C: Partly whitened or uneven on the surface (3) Evaluation of resist pattern (3-1) 5 μmL & S
The developed resist pattern was observed with an optical microscope to confirm the presence or absence of 5 μm line and space, and evaluated according to the following criteria.
A: Confirmation C: Unable to confirm (3-2) 100 nm L & S
The resist pattern after development was observed with an electron microscope, and the presence or absence of the formation of 100 nm L & S line and space was confirmed and evaluated according to the following criteria.
A: Confirmation C: Cannot confirm

Compound (A)
C-1: Calix resorcinarene derivative (Production method: JP-A-9-236919)

Compound (B)
R-1: Irgacure 907 (2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba 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., Inc.)
S-4: N, N-dimethylacetamide (Kanto Chemical Co., Inc.)
S-5: Methylene chloride (Kanto Chemical Co., Inc.)
S-1 / S-3: S-1 / S-3 (weight ratio 4/10) mixed solvent

Claims (30)

A resist composition containing at least one resist compound (A) that satisfies all the conditions (a) to (d), wherein the resist compound (A) is represented by the following formulas (1), (2), (3): Or the resist composition which is a compound represented by (7).
(A) Crosslinking that causes a crosslinking reaction directly or indirectly by irradiation 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. Has at least one reactive group in the molecule.
(B) The molecule has one or more functional groups selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
(C) The molecular weight is 500-5000.
(D) It has a branched structure.

[In the formula (1), X represents the following formula (II) or (III) :

And having at least 3 X in formula (1);
E is a C1-C12 divalent acyclic hydrocarbon group, a C3-C12 divalent cyclic hydrocarbon group, or a C1-C12 substituted alkylene group;
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 formula (II) or (III) , A is a hydrogen atom or a substituent selected from the group consisting of an allyloxy group, an acryloyloxy group, a glycidyloxy group, and a chloromethyloxy group, One is a substituent selected from the group consisting of an allyloxy group, an acryloyloxy group, a glycidyloxy group, and a chloromethyloxy group ;
m is an integer of 1-2 . ]]

[In the formula (2), X is the same as described above, a plurality of X may be the same or different, and G represents the following formulas (i) to (v):

A characteristic group derived from any of the structures
X is bonded to three or more aromatic rings or aliphatic rings in formulas (i) to (v),
v represents an integer of 3 to 15.
{In the formulas (i) to (ii), R represents 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. A substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12; R ² is a hydrogen atom, a hydroxyl group, an acyclic hydrocarbon group having 1 to 12 carbon atoms, or a cyclic hydrocarbon having 3 to 12 carbon atoms Group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi):

(In the formula (vi), ^{E 2} is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, divalent cyclic hydrocarbon group or a substituted alkylene group having 1 to 12 carbon atoms, 3 to 12 carbon atoms Wherein 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 a substituent selected from the group consisting of characteristic groups They may be the same or different; in formulas (iv) to (v), E ′ may be the same or different and each independently represents a single bond or 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 represented, and X is bonded to E ′. }]

[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. And X, E ² and k are the same as defined above,
B is the following formula (vi):

(In formula (vi), X and E ² are the same as 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 11. J is a group selected from the group consisting of —O—, —S—, —NH— and a single bond. However, a plurality of B, E ¹ , E ¹ ′, E ² , and J may be the same or different. ]

(In formula (7), E ² , X and k are the same as above.)   The resist composition according to claim 1, wherein the resist compound (A) has two or more crosslinking reactive groups in the molecule. The resist composition according to claim 1, wherein the branched structure is a structure satisfying at least one of the following (1) to (5).
(1) It has a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure.
(2) It has a quaternary carbon atom.
(3) It contains at least one aromatic ring or aliphatic ring having 3 or more substituents.
(4) It has a tertiary phosphorus atom.
(5) It contains at least one isocyanurate ring. The resist compound (A) is
F ≦ 5 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms).)
The resist composition in any one of Claims 1-3 which satisfy | fills.   The crosslinking reactive group of the resist compound (A) is one or more 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. The resist composition according to any one of claims 1 to 4.   The said crosslinking reactive group of the said resist compound (A) is 1 or more types chosen from the group which consists of a carbon-carbon multiple bond group, an epoxy group, and a halogenated methyl group, The Claim 1-5 Resist composition.   The resist compound (A) has at least one crosslinking reactive group in each branched molecular chain in the branched structure, and a urea bond, a urethane bond, an amide bond, and The resist composition according to claim 1, which has one or more selected from the group consisting of imide bonds.   The resist compound (A) has at least one crosslinking reactive group in each branched molecular chain in the branched structure, and is selected from the group consisting of a urea bond and a urethane bond in each molecular chain The resist composition according to any one of claims 1 to 7, which has one or more selected from the above. The resist composition according to claim 1, wherein the resist compound (A) has a nitrogen content of 1 to 30% by mass. The resist composition according to any one of claims 1 to 9, wherein the compound of the formula (1) is a compound represented by any one of the formulas (4) to (6).



(In formulas (4) to (6), X and E are the same as above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (9).

(In formula (9), X and R ² are the same as above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (10).

(In formula (10), X is the same as above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (11).

(In formula (11), X and k are the same as above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (12).

(In formula (12), X is as defined above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (13).

(In formula (13), X is the same as above) The resist composition according to claim 1, wherein the compound of the formula (2) is a compound represented by the following formula (14).

(In formula (14), X is as defined above) The resist composition according to claim 1, wherein the compound of the formula (3) is a compound represented by the following formula (8).

(In the formula (8), R ³ , E ² , 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.) The resist composition according to any one of claims 1 to 17 , comprising two or more resist compounds (A). Furthermore, radicals or cations are generated directly or indirectly by irradiation 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. the resist composition according to any one of claims 1 to 18 including a compound (B). Further carbon - carbon multiple bond group, a cyclopropyl group, an epoxy group, claims 1 to 19 containing an azide group, halogenated phenyl group, and compounds having one or more selected from the group consisting of methyl halide group, or resin The resist composition according to any one of the above. In the total solid content of the resist composition, the resist compound (A) 40 to 99.998% by weight, the compound (B) 0.001 to 10% by weight, and the other components (C) 0.001 to 50% by weight. The resist composition according to claim 19 or 20 . The resist composition according to claim 19 or 20 , which is 90 to 99.999% by weight of the resist compound (A) and 0.001 to 10% by weight of the compound (B) in the total solid content of the resist composition. The resist composition according to any one of claims 1 to 18 , which is 100% by weight of the resist compound (A) in the total solid content of the resist composition. A resist compound represented by the following formula (1).

[In the formula (1), X represents the following formula (II) or (III) :

And having at least 3 X in formula (1);
E is a C1-C12 divalent acyclic hydrocarbon group, a C3-C12 divalent cyclic hydrocarbon group, or a C1-C12 substituted alkylene group;
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 formula (II) or (III) , A is a hydrogen atom or a substituent selected from the group consisting of an allyloxy group, an acryloyloxy group, a glycidyloxy group, and a chloromethyloxy group, One is a substituent selected from the group consisting of an allyloxy group, an acryloyloxy group, a glycidyloxy group, and a chloromethyloxy group ;
m is an integer of 1-2 . ]] The resist compound according to claim 24 , wherein the compound of the formula (1) is a compound represented by any one of the formulas (4) to (6).



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

[In the formula (2), X is the same as described above, a plurality of X may be the same or different, and G represents the following formulas (i) to (v):

A characteristic group derived from any of the structures
X is bonded to three or more aromatic rings or aliphatic rings in formulas (i) to (v),
v represents an integer of 3 to 15.
{In the formulas (i) to (ii), R represents 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. A substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12; R ² is a hydrogen atom, a hydroxyl group, an acyclic hydrocarbon group having 1 to 12 carbon atoms, or a cyclic hydrocarbon having 3 to 12 carbon atoms Group, a substituted alkyl group having 1 to 12 carbon atoms, and the following formula (vi):

(In the formula (vi), ^{E 2} is a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, divalent cyclic hydrocarbon group or a substituted alkylene group having 1 to 12 carbon atoms, 3 to 12 carbon atoms Wherein 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 a substituent selected from the group consisting of characteristic groups They may be the same or different; in formulas (iv) to (v), E ′ may be the same or different and each independently represents a single bond or 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 represented, and X is bonded to E ′. ]}] 27. The resist compound according to claim 26 , wherein the compound of the formula (2) is a compound represented by any of the following formulas (9) to (14).

(In formula (9), X and R ² are the same as above)

(In formula (10), X is the same as above)

(In formula (11), X and k are the same as above)

(In formula (12), X is as defined above)

(In formula (13), X is the same as above)

(In formula (14), X is as defined above) A resist compound represented by the following formula (3).

[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. And X, E ² and k are the same as defined above,
B is the following formula (vi):

(In formula (vi), X and E ² are the same as 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 11. J is a group selected from the group consisting of —O—, —S—, —NH— and a single bond. However, a plurality of B, E ¹ , E ¹ ′, E ² , and J may be the same or different. ] The resist compound according to claim 28, wherein the compound of the formula (3) is a compound represented by the following formula (8).

(In the formula (8), R ³ , E ² , 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.) A resist compound represented by the following formula (7).

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