JP2005309423A - Resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resist composition adaptable not only to ultraviolet lights such as an i-line and a g-line but to such radiations as visible lights, excimer lasers of KrF, etc., electron beams, X-rays and ion beams. <P>SOLUTION: The resist composition contains a resist compound (A), an acid generator (B) and an acid crosslinking agent (C). The resist compound (A) has (a) one or more substituents of one or more kinds selected from the group consisting of hydroxyl groups, mercapto groups and amino groups in a molecule; has (b) one or more substituents of one or more kinds selected from the group consisting of urea groups, urethane groups, amide groups and imide groups in a molecule; has (c) a molecular weight of 500-5,000; and has (d) a branched structure. The acid generator (B) directly or indirectly generates an acid when irradiated with any radiation selected from the group consisting of visible lights, ultraviolet lights, excimer lasers, electron beams, X-rays and ion beams, and induces a crosslinking reaction between the resist compound (A) and the acid crosslinking agent (C). In this connection, a portion exposed to the radiation is insolubilized. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a radiation-sensitive resist composition containing a resist compound represented by a specific chemical structural formula, an acid generator, and an acid crosslinking agent, which are useful as an acid amplification type non-polymeric resist material. The resist composition of the present invention is used as a radiation-sensitive material that is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, for masks used in the manufacture of LSIs and VLSIs in the electronics field.

  Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, 0.1 μm is obtained by irradiating ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. to 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. About a line pattern 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 the lithography using the conventional 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 fullerene, (2) positive and negative resists derived from calixarene, and (3) derived from starburst compounds. A positive resist, (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 the central skeleton.

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 due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so 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 it cannot be said that it is practical (see Patent Document 14). .
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 Proceedings of SPIE vol. 3999 (2000) P1202-1206.

  An object of the present invention is to provide a radiation-sensitive resist composition that can be used not only for ultraviolet rays such as i-rays and g-rays but also for excimer laser light such as visible rays and KrF, electron rays, X-rays, and ion beams. It is to provide. Still another object of the present invention is to provide a non-polymeric radiation-sensitive resist composition having high sensitivity, high resolution, high heat resistance and solvent solubility by a simple production process.

As a result of intensive studies, the present inventors have found that a composition comprising a compound that satisfies a specific chemical structural condition, an acid generator that directly or indirectly generates an acid upon irradiation with radiation, and an acid crosslinking agent is described above. It was found useful for solving the problem.
That is, the present invention provides all conditions (a) to (d):
(A) The molecule has one or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group,
(B) the molecule has one or more substituents selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group,
(C) selected from the group consisting of a resist compound (A) having a molecular weight of 500 to 5000 and (d) having a branched structure, visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam The present invention relates to a resist composition comprising an acid generator (B) that generates an acid directly or indirectly upon irradiation with any radiation, and an acid crosslinking agent (C).
Furthermore, the present invention provides a resist substrate in which a resist film made of the resist composition is formed on the substrate, and a pattern-formed substrate in which the resist film made of the resist composition is patterned.
Furthermore, the present invention provides a step of forming a resist film by applying the resist composition on a substrate, and the resist film is any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam. And a step of developing the exposed resist film using a developer after the heat treatment as necessary, and a method for forming a resist pattern.
Further, the present invention provides a step of coating the resist composition on a substrate to form a resist film, a step of heat-treating the resist film, and applying the heat-treated resist film to visible light, ultraviolet light, excimer laser, electron beam, X A step of irradiating and exposing any radiation selected from the group consisting of a line and an ion beam, and a step of developing the exposed resist film with an alkali developer after heat treatment as necessary. A resist pattern forming method is provided.
Furthermore, the present invention provides a pattern wiring substrate obtained by etching the pattern forming substrate.

  Since the resist composition of the present invention has high sensitivity, a high-resolution resist pattern can be produced, and a highly integrated semiconductor device can be produced with high productivity.

Hereinafter, the present invention will be described in detail.
The resist composition of the present invention contains a resist compound (A), an acid generator (B), and an acid crosslinking agent (C). The resist compound (A) in the present invention satisfies all the following conditions (a) to (d) simultaneously.

(A) The molecule has one or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group.
By satisfying the condition (a), the resist compound is subjected to an intramolecular and / or intermolecular crosslinking reaction between the acid crosslinking agent (C) and one or more selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group. The exposed portion can be selectively insolubilized in a solvent, and is used for 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 resist compound is preferable because it is soluble in an alkaline aqueous solution and can be developed with an alkaline developer which is an environmentally friendly developer. The molecule has at least 1, preferably 2, more preferably 2 to 15, particularly preferably 3 to 15 hydroxyl groups, mercapto groups, or amino groups. By setting it within the above range, the resolution and alkali development performance can be further improved. Of the hydroxyl group, mercapto group and amino group, a hydroxyl group is preferred, and a phenolic hydroxyl group is particularly preferred.

(B) The molecule has one or more substituents selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group.
The resist compound is one or more substituents selected from the group consisting of a urea group, an amide group, a urethane group, and an imide group, particularly one or more substituents selected from the group consisting of a urea group, an amide group, and a urethane group. It is preferable that 3 or more are included. Moreover, the functional group which has nitrogen components other than the above may be included. As functional groups other than the above, tertiary amino groups; quaternary ammonium groups; imino groups; azide groups; heterocyclic structures containing nitrogen atoms such as pyridine, pyrrole, imidazole, indole, quinoline, pyrimidine, triazine, pyrrolidine, morpholine, etc. Include, but are not limited to, functional groups. In addition, it is preferable that a basic functional group is not included. 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.

(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 resist film-forming properties, and further improve resolution and alkali development performance.

(D) It has a branched structure.
In the present invention, the “branched structure” means the following (1) to (4):
(1) having a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure,
(2) having a quaternary carbon atom,
(3) It contains at least one aromatic ring or aliphatic ring having 3 or more substituents.
(4) having a tertiary phosphorus atom,
(5) including at least one isocyanurate ring,
The chemical structure that satisfies at least one condition.
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)). Further, F is preferably 4.0 or less, and F is preferably 2.5 or more and 4.0 or less. When F is 5 or less, it is possible to prevent deterioration in performance such as sensitivity, resolution, and etching resistance.

  In the present invention, the resist compound (A) has at least one phenolic hydroxyl group in each molecular chain of the branched structure, and a urea bond, a urethane bond, an amide bond, and an imide bond in each molecular chain of the branched structure It is preferable to have one or more bonds selected from the group consisting of:

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

（式（１）中、Ｘは水素、または下記式（Ｉ）：

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

で表され、Ｘのうち少なくとも３つは式（Ｉ）であり；
Ｅは、炭素数１〜１２の二価の非環状炭化水素基、炭素数３〜１２の二価の環状炭化水素基、または炭素数１〜１２の置換アルキレン基を表し；
ｓ、ｔ、ｕはそれぞれ独立して０〜３の整数を表す。但し、複数個のＥ、Ｘ、Ｚ、Ｙは、各々同一でも異なっていてもよい。）
式（Ｉ）において、Ｒ^１は、水素原子、または、炭素数１〜１２の直鎖状炭化水素基、炭素数３〜１２の環状炭化水素基、炭素数１〜１２のアルコキシ基、および炭素数３〜１２の１−分岐アルキル基からなる群から選ばれる置換基であり；
Ａは、水素または水酸基を表し、Ａのうち少なくとも一つは水酸基であり；
Ａｒは炭素数６〜１２の芳香族炭化水素基を表し；
Ｙは炭素数１〜１２の二価の非環状炭化水素基、炭素数３〜１２の二価の環状炭化水素基、炭素数１〜１２の置換アルキレン基、または単結合を表し；
Ｚは単結合、または、−Ｏ−、−Ｓ−および−ＮＨ−からなる群から選ばれる基を表し；
ａ１は１〜９の整数であり；
ｒ１は０〜８の整数であり；
ａ１＋ｒ１≦９であり；
ｎは１〜５の整数である。但し、ｎが２〜５の整数である場合、複数個のＲ^１、Ａ、Ａｒ、ａ１、ｒ１は、各々同一でも異なっていてもよい。

Wherein at least three of X are of formula (I);
E represents a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;
s, t and u each independently represents an integer of 0 to 3. However, the plurality of E, X, Z, and Y may be the same or different. )
In the formula (I), R ¹ represents a hydrogen atom or 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 of 3 to 12;
A represents hydrogen or a hydroxyl group, and at least one of A is a hydroxyl group;
Ar represents an aromatic hydrocarbon group having 6 to 12 carbon atoms;
Y represents 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 group 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 an integer of 1-5. However, when n is an integer of 2 to 5, a plurality of R ¹ , A, Ar, a 1 and r 1 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 produced by reacting an isocyanurate derived from a diisocyanate and an aminophenol or hydroxyalkylphenol. By using isocyanurate derived from diisocyanate, a branched polyphenol compound can be easily obtained.

  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 preferable, tolylene diisocyanate, bis (isocyanate phenyl) methane, isophorone diisocyanate, And isocyanurates derived from bis (isocyanatomethyl) cyclohexane are particularly preferred.

  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 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 of the isocyanurate with aminophenols or hydroxyalkylphenols is carried out by dissolving the aminophenols or hydroxyalkylphenols in an aprotic polar solvent and then adding the isocyanurate dissolved in the aprotic polar solvent. In addition, aminophenols or hydroxyalkylphenols dissolved in an aprotic polar solvent are added to isocyanurate dissolved in an aprotic polar solvent, and then stirred for about 5 minutes to 24 hours. 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, after adding distilled water to the reaction solution to precipitate crystals, washing with distilled water and / or purification with a column chromatograph, high performance liquid chromatograph, and the like, followed by drying, the branched polyphenol compound (of formula (1)) Compound) is obtained.

  The aprotic polar solvent used in the above reaction is not particularly limited as long as it dissolves a compound having 3 or more isocyanate groups, aminophenols or hydroxyalkylphenols, and a branched polyphenol compound, which is a product thereof. A 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.

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

式（４）〜（６）中、ＸとＥは前記と同様である。

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

  The compounds of formulas (4) to (6) are produced by reacting isocyanurates derived from diisocyanates and aminophenols or hydroxyalkylphenols. 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.

  The reaction of isocyanurate derived from diisocyanate and aminophenols or hydroxyalkylphenols can be carried out in the same manner as the reaction of the compound having three or more isocyanate groups with aminophenols or hydroxyalkylphenols. it can. 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) to (23) are particularly preferable.

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

（式（２）中、Ｘは前記と同様であり、複数のＸは同一でも異なっていてもよく、Ｇは式（ｉ）〜（ｖ)：

(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):

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

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 (iii), R is a hydrogen atom or a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and A substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12 carbon atoms, and R ² is a hydrogen atom, a hydroxyl group, an acyclic hydrocarbon group having 1 to 12 carbon atoms, and a cyclic carbonization group having 3 to 12 carbon atoms. A hydrogen group, a substituted alkyl group having 1 to 12 carbon atoms, and formula (vi):

（式（vi）中、Ｅ^２は炭素数１〜１２の二価の非環状炭化水素基、炭素数３〜１２の二価の環状炭化水素基、または炭素数１〜１２の置換アルキレン基のいずれかである。）
の基からなる群から選ばれる置換基であり、ｒは０〜４の整数であり、ｋは１〜７の整数である。但し、複数個のＲ、ｒは、各々同一でも異なっていてもよい。）

(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.)
The substituent is selected from the group consisting of the following 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.

  The reaction of the monoisocyanate oligomer or triisocyanate with the aminophenol or hydroxyalkylphenol can be carried out in the same manner as the reaction of the isocyanurate derived from the diisocyanate with the aminophenol or hydroxyalkylphenol. it can.

  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 and hydroxyalkylphenols. 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 can be carried out in the same manner as the reaction of isocyanurate derived from the above-mentioned diisocyanates with aminophenols or hydroxyalkylphenols. .

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 and aminophenols or hydroxyalkylphenols. 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 between the isocyanate phenylmethane oligomer and the aminophenol or hydroxyalkylphenol can be carried out in the same manner as the reaction between the isocyanurate derived from the diisocyanate and the aminophenol or hydroxyalkylphenol.

The compound of the formula (12) is produced by reacting mesitylene triisocyanate and aminophenols or hydroxyalkylphenols. 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 and aminophenols or hydroxyalkylphenols. 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 can be carried out in the same manner as the reaction of isocyanurate derived from diisocyanates with aminophenols or hydroxyalkylphenols.

The compound of the formula (14) is produced by reacting cyclohexane triisocyanate and aminophenols or hydroxyalkylphenols. 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 can be carried out in the same manner as the reaction of isocyanurate derived from diisocyanates with aminophenols or hydroxyalkylphenols.

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

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

（式（３）中、Ｒ^３は水素原子、炭素数１〜１２の非環状炭化水素基、炭素数３〜１２の環状炭化水素基、および炭素数１〜１２の置換アルキル基からなる群から選ばれる置換基であり、Ｘ、Ｅ^２およびｋは前記と同様であり、Ｂは式（vi）：

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

（式（vi）中、ＸとＥ^２は前記と同様である。）
で表される基または水素原子であり、Ｅ^１及びＥ^１’は、同一でも異なっていてもよく、それぞれ独立して単結合又は炭素数１〜１１の２価の炭化水素基を表す。ただし、Ｅ^１とＥ^１’の炭素数の合計は０〜１１である。Ｊは−Ｏ−、−Ｓ−、−ＮＨ−および単結合からなる群から選ばれる基である。但し、複数個のＢ、Ｅ^１、Ｅ^１’、Ｅ^２、Ｊは、各々同一でも異なっていてもよい。）

(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 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 the formula (vi) are represented by the following formula (1): The same 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, and aminophenols or hydroxyalkylphenols. A branched polyphenol compound can be easily obtained by using a burette body, an allohanate body, or a urethane body derived from diisocyanate.

  The burette, allophanate or urethane derived from diisocyanate is not particularly limited, but tolylene diisocyanate, bis (isocyanatephenyl) 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 them, 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 of a burette body, allophanate body or urethane body derived from diisocyanate with aminophenols or hydroxyalkylphenols is the reaction of isocyanurate derived from diisocyanate with aminophenols or hydroxyalkylphenols. It can be performed in the same way.

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

（式中Ｒ^３、Ｅ^２、Ｘ、Ｊ、ｋは前記と同様である。但し、複数個のＲ^３、Ｅ^２、Ｘ、Ｊは、各々同一でも異なっていても良い。）
Ｒ^３が表す炭素数１〜１２の非環状炭化水素基、炭素数３〜１２の環状炭化水素基、および炭素数１〜１２の置換アルキル基としては、式（１）と同じものが例示できる。

(In the formula, R ³ , E ² , X, J, and k are the same as described above, provided that a plurality of R ³ , E ² , X, 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 are the same as those in the formula (1). .

  The compound of the formula (8) is produced by reacting a urethane compound derived from diisocyanate and aminophenols or hydroxyalkylphenols. By using a urethane body derived from diisocyanate, a branched polyphenol compound can be easily obtained.

  The urethane body 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 the urethane compound derived from diisocyanate and aminophenols or hydroxyalkylphenols can be carried out in the same manner as the reaction between the isocyanurate derived from diisocyanate and aminophenols or hydroxyalkylphenols. it can.

  Of the compounds represented by the formula (8), a compound represented by the following formula (24) is particularly preferable.

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

（式（７）中、Ｅ^２、Ｘおよびｋは前記と同様である。）

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

  The compound of the formula (7) is produced by reacting a burette body derived from diisocyanate and aminophenols or hydroxyalkylphenols. 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 one 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 between the buret derivative derived from diisocyanate and aminophenols or hydroxyalkylphenols should be carried out in the same manner as the reaction between the above-mentioned isocyanurates derived from diisocyanates and aminophenols or hydroxyalkylphenols. Can do.

  Of the compounds represented by the formula (7), a compound represented by the following formula (25) is 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).

（式（II）〜（III）中、Ａは前記と同様であり、ｍは１〜２の整数である。）

(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 3 or more isocyanate groups and aminophenols. 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) in the present invention 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) in the present invention is preferably dissolved in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or ethyl lactate at 23% by weight at 5% by weight or more. By satisfying the above conditions, it is possible to use a safe solvent that can be used in a semiconductor factory.

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

  The resist composition of the present invention comprises an acid generator (B) that generates an acid directly or indirectly by irradiation with radiation selected from visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam. ).

  The resist compound (A) is an acid amplification type compound. When an acid coexists, the acid cross-linking agent (C) and the resist compound (A) are cross-linked between molecules or within the molecule to become an alkali-insoluble material. Since the portion where no acid coexists becomes an alkali-soluble material, it can be used as a negative resist capable of alkali development. The method for generating the acid is not particularly limited. For example, the acid is generated in the exposed portion by irradiation with radiation such as ultraviolet rays or high energy.

  That is, in the present invention, as long as an acid is generated in the system, the method for generating the acid is not limited. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if electron beam, X-ray and ion beam are used as high-energy rays, further fine processing is possible. is there.

  The acid generator (B) is preferably 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 It is at least one selected from the group consisting of lomethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, and diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate. 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, diphenyl Iodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzenesulfonate , Diphenyliodonium Xafluorobenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro- n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, and bis (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate It is preferably at least one selected from the group.

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):

で表わされる置換基、−Ｒ^ａ−Ｃ（＝Ｏ）−Ｒ^ｂ−、−Ｒ^ａ−Ｃ（＝Ｏ）−Ｏ−Ｒ^ｂ−、−Ｒ^ａ−Ｃ（＝Ｏ）−ＮＨ−Ｒ^ｂ−、又は−Ｒ^ｃ−Ｏ−Ｒ^ｄ−（但し、Ｒ^ａとＲ^ｂは同一でも異なっていてもよく、それぞれ独立して単結合又は炭素数１〜３のアルキレン基を表し、Ｒ^ａとＲ^ｂの炭素数の合計は０〜３であり；Ｒ^ｃとＲ^ｄは同一でも異なっていてもよく、それぞれ独立して単結合又は炭素数１〜４のアルキレン基を表し、Ｒ^ｃとＲ^ｄの炭素数の合計は０〜４である）であり、Ｙ^２９は水素原子、炭素原子数１〜３のアルキル基、または炭素原子数６〜１０のアリール基であり、Ｘ^２９およびＸ^３０は、それぞれ下記式（４２）：

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):

式（４２）中、Ｚ^３２はそれぞれ独立に、炭素原子数１〜３のアルキル基、炭素原子数３〜１０のシクロアルキル基、または炭素原子数６〜１０のアリール基であり、Ｒ^３２は炭素原子数１〜３のアルキル基、炭素原子数３〜１０のシクロアルキル基、または炭素原子数１〜３のアルコキシル基であり、ｒは０〜３の整数である。）
で示される基である。

In the formula (42), Z ³² is each independently an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ³² is It 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.

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Bissulfonyldiazomethanes such as 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, tris A halogen-containing triazine derivatives such as 2,3-dibromopropyl) isocyanurate.

  Moreover, the said acid generator (B) can be used individually or in combination of 2 or more types. In the composition of the present invention, the amount of the acid generator 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 by weight per 100 parts by weight of the resist compound. Part. 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 also contains one or more acid crosslinking agents (C). The acid crosslinking agent (C) is a compound that can crosslink the resist compound (A) within a molecule or between molecules in the presence of an acid generated from the acid generator (B). Examples of such a crosslinking agent (C) include compounds having one or more substituents having crosslinking reactivity with the resist compound (A) (hereinafter referred to as “crosslinkable substituents”). .

  Specific examples of such crosslinkable substituents include (i) hydroxyalkyl such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. A group or a substituent derived therefrom; (ii) a carbonyl group such as formyl group, carboxy (C1-C6 alkyl group) or a substituent derived therefrom; (iii) a dimethylaminomethyl group, a diethylaminomethyl group, a di Nitrogen-containing substituents such as methylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) benzyloxy C1-C6 allyloxy (C1-C) such as methyl group, benzoyloxymethyl group 6 alkyl groups), substituents derived from aromatic groups such as C1-C6 aralkyloxy (C1-C6 alkyl groups); (vi) substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. be able to. As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

  Examples of the acid crosslinking agent (C) having a crosslinkable substituent include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, etc. Containing compound; (iii) carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxymethyl group-containing Carboxymethyl group-containing compounds such as recall uril compounds and carboxymethyl group-containing phenol compounds; (iv) bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolak resin epoxy compounds, resole resin epoxy compounds And epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

  As the acid crosslinking agent (C), it is further possible to use a compound having a phenolic hydroxyl group, and a compound and a resin imparted with a crosslinking property by introducing the crosslinking substituent into an acidic functional group in the alkali-soluble resin. it can. The introduction rate of the crosslinkable substituent in that case is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably 10 to 60 mol%, based on the total acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Preferably, it is adjusted to 15 to 40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.

  In the resist composition of the present invention, the acid crosslinking agent (C) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (C) include compounds represented by the following formulas (43) to (45) and alkoxymethylated melamine compounds (acid crosslinking agent (C1)).

In formulas (43) to (45), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group having 2 to 6 carbon atoms is preferably an acyl group having 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. R ^{6 to} R ⁹ in Formula (43) represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² represents a single bond, a methylene group, or an oxygen atom, and preferably a single bond or a methylene group. R ^{5 to} R ⁹ and X ² each have a substituent such as an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group or a halogen atom in addition to the groups exemplified above. You may do it. A plurality of R ⁵ and R ^{6 to} R ⁹ may be the same or different.

  Specific examples of the compound represented by the formula (43) include the compounds shown below.

式（４４）で表される化合物として具体的には、例えば、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（メトキシメチル）グリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（エトキシメチル）グリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（ｎ−プロポキシメチル）グリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（イソプロポキシメチル）グリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（ｎ−ブトキシメチル）グリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（ｔ−ブトキシメチル）グリコールウリル等を挙げることができる。この中で、特に、Ｎ，Ｎ，Ｎ，Ｎ−テトラ（メトキシメチル）グリコールウリルが好ましい。

Specific examples of the compound represented by the formula (44) include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N , N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycol Examples include uril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like. Among these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

  Specific examples of the compound represented by the formula (45) include the compounds shown below.

  Specific examples of the alkoxymethylated melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.

  The acid cross-linking agent (C1) is obtained by, for example, condensing a urea compound or glycoluril compound and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered. The acid cross-linking agent (C1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicarac (manufactured by Sanwa Chemical Co., Ltd.).

  Further, as other particularly preferable acid crosslinking agent (C), the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule, and the hydroxyalkyl group and A phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings can be mentioned (acid crosslinking agent (C2)). Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total, and the hydroxyalkyl group and / or alkoxyalkyl group is the benzene. A phenol derivative formed by bonding to any one or a plurality of benzene rings can be given.

  As a hydroxyalkyl group couple | bonded with a benzene ring, C1-C6 things, such as a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group, are preferable. As an alkoxyalkyl group couple | bonded with a benzene ring, a C2-C6 thing is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl And a 2-methoxy-1-propyl group are preferred.

  Among these phenol derivatives, particularly preferable ones are listed below.

In the above formula, L ^{1 to} L ⁸ may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group. A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

  A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.

  A phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. preferable. The acid crosslinking agent (C2) may be used alone or in combination of two or more.

Another particularly preferable acid crosslinking agent (C) is a compound having at least one α-hydroxyisopropyl group (crosslinking agent (C3)). The structure is not particularly limited as long as it has an α-hydroxyisopropyl group. In addition, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc., R is a straight chain having 1 to 12 carbon atoms) A hydrocarbon group, 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, and an aromatic hydrocarbon group having 6 to 12 carbon atoms Which represents a substituent selected from the group consisting of: Examples of the compound having the α-hydroxyisopropyl group include one or two kinds such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following general formula (46) (hereinafter referred to as “benzene compound (46)”), a compound represented by the following general formula (47) (hereinafter referred to as “diphenyl type”). Compound (47) "), a compound represented by the following general formula (48) (hereinafter referred to as" naphthalene compound (48) "), and a compound represented by the following general formula (49) (hereinafter referred to as" the compound (47) "). "Furan compound (49)").

In the general formulas (46) to (49), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In General Formula (46), R ⁵¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched alkoxy group having 2 to 6 carbon atoms. A carbonyl group is shown. Further, in the general formula (47), R ⁵² represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO—, or —COO—. Moreover, in general formula (49), ^R53 and ^R54 show a hydrogen atom or a C1-C6 linear or branched alkyl group mutually independently.

  Specific examples of the benzene compound (46) include, for example, α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, 1,2 , 4-Tris (α-hydroxyisopropyl) benzene, α-hydroxyisopropylbenzenes such as 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol , 3,5-bis (α-hydroxyisopropyl) phenol, α-hydroxyisopropylphenols such as 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Phenyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Phenyl ethyl ketone, α-hydroxyisopropylphenyl alkyl ketones such as 2,4,6-tris (α-hydroxyisopropyl) phenyl methylketone; 3-α-hydroxyisopropylbenzoic acid , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl N-butyl benzoate, t-butyl 4-α-hydroxyisopropylbenzoate, n-pentyl 4-α-hydroxyisopropylbenzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis Examples include 4-α-hydroxyisopropyl benzoate alkyls such as ethyl (α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

  Specific examples of the diphenyl compound (47) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyiso) Propyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4 , 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl and the like α-hydroxyisopropylbiphenyls; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxy) Isopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α- Hydroxyisopropylphenyl) -3-phenylpropane, 1- 4-α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3′-bis ( α-hydroxyisopropyl) diphenylmethane, 3,4′-bis (α-hydroxyisopropyl) diphenylmethane, 4,4′-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2, , 4,6-Tris (α-hydroxyisopropyl) diphe Lumethane, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) Diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6 Α-hydroxyisopropyldiphenylalkanes such as pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether 4-α-hydroxyisopro Rudiphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis (Α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α- Hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5 ′ -Tetrakis α-hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) Α-hydroxyisopropyl diphenyl ethers such as diphenyl ether; 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α -Hydroxyisopropyl) diphenylketone, 3,4'-bis (α-hydroxyisopropyl) diphenylketone, 4,4'-bis (α-hydroxyisopropyl) diphenylketone, 2,4,6-tris (α-hydroxyisopropyl) Diphenyl , 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxy) Isopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4 , 5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, α-hydroxyisopropyl diphenyl ketones such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ketone; Phenyl 3-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate Phenyl benzoate, 3-α-hydroxyisopropylphenyl benzoate, 4-α-hydroxyisopropylphenyl benzoate, phenyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3-α-hydroxyisopropylbenzoate 3-α -Hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoic acid 4-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid 4-α-hydroxy Isopropyl phenyl, 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3- α-hydroxy Sopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α- 3,5-bis (α-hydroxyisopropyl) phenyl hydroxyisopropylbenzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3 -Α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3,5-bis (α -Hydroxyisopropyl) phenyl, 3-α-hydroxyisopropyl Pyrbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α -Hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4 , 6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl and the like α-hydroxyisopropylbenzoic acid phenyls and the like.

  Further, specific examples of the naphthalene compound (48) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α Hydroxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) And naphthalene.

  Specific examples of the furan compound (49) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) fura 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) ) Furan etc. can be mentioned.

  The acid crosslinking agent (C3) is preferably a compound having two or more free α-hydroxyisopropyl groups, a benzene compound (46) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. More preferred are diphenyl compounds (47) and naphthalene compounds (48) having two or more α-hydroxyisopropyl groups, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, and α-hydroxyisopropyl groups. The naphthalene compound (48) having two or more is particularly preferred.

The acid cross-linking agent (C3) is usually a method of hydrolyzing after a methylation by reacting a acetyl group-containing compound such as 1,3-diacetylbenzene with a Grignard reagent such as CH ₃ MgBr, or 1,3 It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.

  In the present invention, the blending ratio of the acid crosslinking agent (C) is 0.5 to 70 parts by weight, preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight per 100 parts by weight of the resist compound (A). It is. When the blending ratio of the acid crosslinking agent (C) is 0.5 parts by weight or more, the effect of suppressing the solubility of the resin (A) in an alkaline developer is improved, the remaining film ratio is reduced, or the pattern is swollen. And 70 mean by weight or less are preferable because the reduction in heat resistance as a resist can be suppressed.

  Further, the blending ratio of at least one compound selected from the acid crosslinking agent (C1), the acid crosslinking agent (C2), and the acid crosslinking agent (C3) in the acid crosslinking agent (C) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.

  In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compound represented by (44) is 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70 to 98% by weight, still more preferably. It is preferably 80 to 97% by weight. Since the resolution can be improved by setting the alkoxymethylated melamine compound and / or the compound represented by (44) to 50% by weight or more of the total acid crosslinking agent component, preferably by 99% by weight or less, The pattern cross-sectional shape is preferable because it is easy to obtain a rectangular cross-sectional shape.

  The resist composition of the present invention includes, as necessary, an acid diffusion controller, a dissolution controller, a dissolution accelerator, a sensitizer, and an interface as an optional component (D) as long as the object of the present invention is not impaired. One or more additives such as an activator can be added.

[1] Acid Diffusion Control Agent The undesired chemical reaction in the unexposed region is controlled by controlling the diffusion phenomenon in the resist film of the acid generated from the photoacid generator upon irradiation with the resist composition of the present invention. You may mix | blend the acid diffusion control agent which has an effect | action etc. By using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and the holding time before electron beam irradiation and the fluctuation of the holding time after electron beam irradiation are varied. It is possible to suppress the change in the line width of the resist pattern due to the above, and the process stability is extremely excellent.

  Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include the following general formula (50):

で表される化合物（以下、「含窒素化合物（Ｉ）」という。）、同一分子内に窒素原子を２個有するジアミノ化合物（以下、「含窒素化合物（II）」という。）、窒素原子を３個以上有するポリアミノ化合物や重合体（以下、「含窒素化合物（III）」という。）、アミド基含有化合物、ウレア化合物、及び含窒素複素環式化合物等を挙げることができる。尚、上記酸拡散制御剤は、１種単独で用いてもよく、２種以上を併用してもよい。

(Hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), and a nitrogen atom. Examples thereof include polyamino compounds and polymers having three or more (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In the general formula (50), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Specific examples of the nitrogen-containing compound (I) include mono-cyclohexane such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.

  Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) 1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

  Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

  Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can gel.

  Moreover, as a basic compound decomposed | disassembled by the said exposure, the following general formula (51):

で表されるスルホニウム化合物、及び下記一般式（５２）：

A sulfonium compound represented by the following general formula (52):

で表されるヨードニウム化合物等を挙げることができる。

The iodonium compound etc. which are represented by these can be mentioned.

In the general formulas (51) and (52), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyl having 1 to 6 carbon atoms. A group, a hydroxyl group or a halogen atom; Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an alkaryl group having 1 to 6 carbon atoms) or the following general formula. (53):

で表されるアニオンを示す。

An anion represented by

  Specific examples of the basic compound that decomposes upon exposure include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, and diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydro Oxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4- hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

  The compounding amount of the acid diffusion controller is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight, still more preferably 0.01 to 3 parts by weight per 100 parts by weight of the resist compound (A). It is. By making the blending amount 0.001 part by weight or more, resolution, pattern shape, dimensional fidelity, etc. are further improved, and even if the holding time from electron beam irradiation to heating after radiation irradiation becomes long, The pattern shape of the pattern upper layer portion can be improved. When the blending amount is 10 parts by weight or less, it is possible to prevent the resist sensitivity, the developability of the unexposed part, and the like from being lowered.

[2] Solubility control agent The solubilization control agent acts to moderately reduce the dissolution rate during development by controlling the solubility of the resist compound (A) in a developing solution such as alkali. It is a component that has. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.

  Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.

  The blending amount of the dissolution control agent is appropriately adjusted according to the type of the resist compound (A) to be used, but 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 (A). It is.

[3] Dissolution Accelerator The dissolution accelerator increases the solubility of the resist compound (A) during development when the solubility of the resist compound (A) in a developing solution such as alkali is too low. It is a component having an action of increasing moderately. Examples of the dissolution accelerator include low molecular weight phenolic compounds having about 2 to 6 benzene rings, and specific examples include bisphenols, tris (hydroxyphenyl) methane, and the like. it can. These dissolution promoters can be used alone or in admixture of two or more.

  The blending amount of the dissolution accelerator is appropriately adjusted according to the type of the resist compound (A) to be used, but 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 (A). It is.

[4] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (B), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.

  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 (A).

[5] 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 of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. The nonionic surfactant has a good affinity with the solvent used in the production of the radiation-sensitive resist composition and is more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products include the following product names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink & Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and the like.

  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 (A).

[6] Additives other than the above acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, and surfactant Further, the negative radiation-sensitive resist composition of the present invention has the object of the present invention. One or more additives other than the acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, and surfactant can be blended as necessary within the range not inhibiting. Examples of such additives include dyes, pigments, and adhesion aids. 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. The total solid concentration in the homogeneous solution is usually 50% by weight or less, preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and still more preferably 1 to 10% by weight.

  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 acids 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, ethyl pyruvate; aromatic hydrocarbons such as toluene, 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 can contain a compound and / or resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Although it does not specifically limit as a compound soluble in alkaline aqueous solution, For example, the phenolic compound which has phenolic hydroxyl groups, such as a polyphenol compound, is mentioned, As a resin soluble in alkaline aqueous solution, a novolak resin, polyvinylphenols , Polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or derivatives thereof.
In addition, a vinyl group which is a cross-linking reactive group that causes a cross-linking reaction by irradiation with visible light, ultraviolet light, excimer laser, electron beam, X-ray and ion beam or a chemical reaction induced thereby without departing from the object of the present invention. , An allyl group, a cinnamoyl group, a vinylsilyl group, an epoxy group, a chloromethyl group, a halogenated phenyl group, and / or a resin. The compound and / or resin having a crosslinking reactive group is not particularly limited, and is produced by reacting a compound and / or resin that is soluble in the alkaline aqueous solution with a crosslinking reactive group introduction reagent in the presence of a base catalyst. Compounds and / or polymers, or derivatives thereof. 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. One or more of these may be used.

  The composition of the resist composition of the present invention (resist compound (A) / acid generator (B) / acid cross-linking agent (C) / optional component (D)) is weight% based on solids, preferably 3 to 96. 9.9 / 0.1-30 / 3-65 / 0-93.9, more preferably 65-96.9 / 0.1-30 / 0.3-34.9 / 0-30, more preferably 65 -96.9 / 0.1-30 / 0.3-34.9 / 0-10, particularly preferably 65-96.9 / 0.1-30 / 0.6-34.9 / 0-5, Most preferably, it is 65-96.9 / 0.1-30 / 0.6-30 / 0. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.

  In the present invention, the resist substrate is a substrate in which a resist film made of the resist composition is formed on a substrate, and the pattern formation substrate is a pattern in which the resist film on the resist substrate is patterned by exposure and development. It is a substrate. The “pattern forming material” refers to a composition formed on a resist substrate and capable of forming a pattern by irradiation with light, an electron beam or radiation, and is synonymous with “resist film”. A “pattern wiring substrate” is a substrate having a patterned wiring obtained by etching a pattern forming substrate.

  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. Although heating conditions change with the compounding composition of a radiation sensitive resist composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. 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, electron beam, X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation-sensitive resist 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. Although heating conditions change with the compounding composition of a radiation sensitive resist composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.

  Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution in which one or more compounds are dissolved so as to have a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.

  In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

  After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

  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 residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. As the strong alkaline aqueous solution, for example, 1 to 20% by mass of sodium hydroxide aqueous solution or 1-20 mass% potassium hydroxide aqueous solution is mentioned. 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 the present invention can also be formed by a method of depositing a metal in 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.

Each measurement method is shown below.
(1) Nitrogen content of the compound: determined by CHN elemental analysis.
(2) Molecular weight of the compound: The substance identified by IR and ¹ H-NMR was calculated.
(3) Compound factor (F): determined by calculation.
(4) Evaluation of film formability of resist film A 10 × 10 mm square resist film was divided into 100 sections, and the sections not covered by the resist film and the sections crystallized were counted and evaluated according to the following criteria.
Zero: + (good)
1 or more:-(defect)
(5) 5μmL & S of resist pattern
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.
Confirmation: +
Cannot confirm: −
(6) Substrate adhesion of resist pattern A 10 × 10 mm square resist film was divided into 100 sections, and the sections where the resist film was peeled off were counted and evaluated according to the following criteria.
Zero: + (good)
1 or more:-(defect)
(7) Resistance to etching of resist pattern An Al / Si / Cu alloy thin film (about 200 nm) was deposited on a silicon wafer using a SH-550 type high-rate sputtering apparatus manufactured by Japan Vacuum Technology. A resist composition was applied on the thin film to form a resist film. The resist film was subjected to pattern exposure and development to form a resist pattern. Next, after etching under the following conditions, the resist was washed with pure water and the residual resist was dissolved with acetone.
Etching solution: 0.1N sodium hydroxide aqueous solution Etching time: 3 min
The etching pattern was observed with an optical microscope, and the shape of the pattern was judged visually.
Good: +
Defect:-

Synthesis Example 1 Production of TDIAP (Compound (19)) A solution of tolylene diisocyanate isocyanurate (TDI) in 50% by weight of butyl acetate (Bernock D-800, manufactured by Dainippon Ink Industries, Ltd., NCO equivalent: 592, nonvolatile content: 51% by weight) ) 10 ml of dimethylacetamide (DMAc) (a reagent manufactured by Kanto Chemical Co., Inc.) was added to 17.34 g. The obtained solution was slowly dropped into a DMAc 10 ml solution of 3.27 g (30 mmol) of p-aminophenol (AP) (a reagent manufactured by Kanto Chemical Co., Ltd.) using a dropping funnel 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 again added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 20.1 g of a product. The structure was confirmed to be the formula (19) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 14.8%, the molecular weight was 849.3, and the factor (F) was 2.8.
IR: (cm ⁻¹ )
3413 (O—H stretching vibration), 1702 (C═O, carbonyl)
¹ H-NMR: (400 MHz, CDCl ₃ , internal standard TMS)
δ (ppm): 7.0 to 8.1 (Ph— H ), 3.5 (—C (C H ₃ ) ₃ ), 2.1 to 2.4 (Ph—C H ₃ ), 9.3 (—O H ), 9.0 to 9.1 (—N H —)

Synthesis Example 2 Production of TDIDHBA (Compound (21)) A solution obtained by adding 20 ml of DMAc to 17.34 g of a 50% by weight butyl acetate solution of TDI was added to a 3,5-dihydroxybenzyl alcohol (DHBA) (manufactured by ACROS) using a dropping funnel. Reagent) The solution was slowly added dropwise to a solution of 4.20 g (30 mmol; 1.0 equivalent) of DMAc in 30 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 a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 21.1 g of a product. The structure was confirmed to be the formula (21) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 8.9%, the molecular weight was 942.3, and the factor (F) was 3.4.
IR: (cm ⁻¹ )
3355 (O—H stretching vibration), 1708 (C═O, carbonyl)
¹ H-NMR: (400 MHz, CDCl ₃ , internal standard TMS)
δ (ppm): 7.0 to 8.3 (Ph— H ), 1.49 (—C (C H ₃ ) ₃ ), 2.1 to 2.4 (Ph—C H ₃ ), 3.34 (Ph—C H ₂ —O—), 9.1 (—N H —), 9.0 (—O H )

Synthesis Example 3 Production of TPMTIAP (Compound (26)) 27 wt% solution of triphenylmethane triisocyanate (TPMTI) in ethyl acetate / monochlorobenzene (70/3) (Bayer Desmodur RE, NCO equivalent: 441, nonvolatile content: (27 wt%) A solution obtained by adding 3 ml of DMAc to 2.21 g was slowly dropped into a solution of 0.55 g (5 mmol, 1.0 equivalent) of DMAc in 5 ml using a dropping funnel and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 1.02 g of a product. The structure was confirmed to be the formula (26) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 12.1%, the molecular weight was 694.3, and the factor (F) was 2.7.
IR: (cm ⁻¹ )
3307 cm ⁻¹ (O—H stretching vibration), 1648 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.5 to 7.4 ppm (Ph— H ), 5.4 ppm (—C H =), 8.3 to 8.6 ppm (—N H —), 9.0 (—O H )

Synthesis Example 4 Production of TPMTIDHBA (Compound (27)) 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) was added using a dropping funnel, 0.70 g (5 mmol, 1.0 equivalent) of DMAc in 5 ml, and slowly 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 again added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 1.51 g of a product. The structure was confirmed to be the formula (27) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 5.3%, the molecular weight was 787.2, and the factor (F) was 3.1.
IR: (cm ⁻¹ )
3295 cm ⁻¹ (O—H stretching vibration), 1697 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.8 to 7.4 ppm (Ph— H ), 5.0 ppm (—C H ₂ —), 6.1 ppm (—C H =), 9.8 ppm (—N H —), 9 .3 (-O H )

Synthesis Example 5 Production of MDIAP (Compound (29)) Polymethylene polyisocyanate (MDI) (Sumidur 44V20, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 135, nonvolatile content: 100% by weight) 2.70 g of DMAc 5 ml The added solution was slowly added dropwise to a DMAc 5 ml solution of AP 2.18 g (20 mmol, 1.0 equivalent) using a dropping funnel and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 4.23 g of a product. The structure was confirmed to be the formula (29) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 11.9%, the molecular weight was 708.3, and the factor (F) was 2.6.
IR: (cm ⁻¹ )
3298 cm ⁻¹ (O—H stretching vibration), 1641 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.6 to 7.4 ppm (Ph— H ), 3.8 to 3.9 ppm (—C H ₂ —), 8.2 to 8.5 ppm (—N H —), 9.1 (-O H )

Synthesis Example 6 Production of BICAP (Compound (20)) 2039 g of bisisocyanatocyclohexane (reagent manufactured by Kanto Chemical Co., Ltd.) was stirred at 50 ° C., and tetramethylammonium diethylhexanoate ethyl cellosolve solution (as a catalyst) DABCO / TMR) (manufactured by Nippon Emulsifier Co., Ltd.) (2.2 g) was added dropwise over 20 minutes. Thereafter, the reaction was followed by gel permeation chromatography (hereinafter abbreviated as GPC) while stirring at 70 ° C., and when the isocyanurate conversion rate reached 40%, phosphoric acid (Kanto Chemical Co., Ltd.) was used as a reaction terminator. Reagents manufactured by 0.35 g were added. The reaction liquid cooled to 50 ° C. was filtered to remove the catalyst and the reaction terminator salt, followed by thin-film distillation using a thin-film distillation apparatus. The composition was confirmed by GPC. The isocyanurate content was 99.99. 2% 739 g of bisisocyanatocyclohexane isocyanurate (BIC) was obtained. Thereafter, a 71.8% by weight butyl acetate solution was prepared. A solution of BIC in butyl acetate (NCO equivalent: 324, nonvolatile content: 71.8% by weight) 6.50 g of DMAc 5 ml was added to a solution of AP 2.18 g (20 mmol, 1.0 equivalent) in DMAc 5 ml using a dropping funnel. The solution was slowly added dropwise and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 4.55 g of a product. The structure was confirmed to be the formula (20) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 13.9%, the molecular weight was 909.5, and the factor (F) was 3.3.
IR: (cm ⁻¹ )
3299 cm ⁻¹ (O—H stretching vibration), 1689 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 7.1~7.3ppm (Ph- H), 0.6~1.7ppm (Ch- H), 2.4~4.0ppm (-C H 2 -), 6.0, 7.9 ppm (-N H- ), 8.9 (-O H )

Synthesis Example 7 Production of IPDIAP (Compound (22)) Isophorone diisocyanate isocyanurate (IPDI) 70% by weight solution of butyl acetate (Degussa, NCO equivalent: 358, nonvolatile content: 70% by weight) 7.16 g of DMAc 5 ml Using a dropping funnel, the solution added was slowly added dropwise to a solution of AP2.19 g (20 mmol, 1.0 equivalent) in 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 filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 4.34 g of a product. The structure was confirmed to be the formula (22) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 12.7%, the molecular weight was 993.6, and the factor (F) was 3.3.
IR: (cm ⁻¹ )
3299 cm ⁻¹ (O—H stretching vibration), 1691 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.9 to 7.4 ppm (Ph— H ), 0.9 to 1.4 ppm (—C H ₃ ), 1.0 to 1.6, 3.7 ppm (Ch— H ), 3 .6 ppm (—C H ₂ —), 8.4 to 8.5 ppm (—N H —), 8.9 (—O H )

Synthesis Example 8 Production of TDIMTPAP (Compound (24)) Trimethylolpropane adduct body (TDITMP) of tolylene diisocyanate 75% by weight in ethyl acetate (Sumidur L75 manufactured by Sumika Bayer Urethane Co., Ltd., NCO equivalent: 324, non-volatile (Min: 75 wt%) A solution obtained by adding 5 ml of DMAc to 3.16 g was slowly dropped into a DMAc 5 ml solution of AP 1.09 g (10 mmol, 1.0 equivalent) using a dropping funnel, and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 2.66 g of a product. The structure was confirmed to be the formula (24) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 12.8%, the molecular weight was 983.4, and the factor (F) was 3.2.
IR: (cm ⁻¹ )
3293 cm ⁻¹ (O—H stretching vibration), 1700, 1652 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.7 to 8.0 ppm (Ph— H ), 0.9 ppm (—C H ₃ ), 2.2 ppm (—C H ₂ —), 4.1 ppm (—C H ₂ —), 9.1-9.6 ppm (-N H- ), 8.7 (-O H )

Synthesis Example 9 Production of HDIAP (Compound (25)) A methoxypropyl acetate / xylene 75 wt% solution of hexamethylene diisocyanate burette (HDI) (Sumidule N75, Sumika Bayer Urethane Co., Ltd., NCO equivalent: 255, (Nonvolatile content: 75% by weight) A solution obtained by adding 5 ml of DMAc to 2.62 g was slowly dropped into a DMAcml solution of 1.09 g (10 mmol, 1.0 equivalent) of AP using a dropping funnel and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 2.10 g of a product. The structure was confirmed to be the formula (25) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 15.6%, the molecular weight was 805.5, and the factor (F) was 3.5.
IR: (cm ⁻¹ )
3307 cm ⁻¹ (O—H stretching vibration), 1672, 1616 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.6 to 7.2 ppm (Ph— H ), 1.2 ppm (—C H ₃ ), 1.2 to 2.0 ppm (—C H ₂ —), 3.6 ppm (—C H _2- ), 5.9 ppm (—N H —), 8.0 to 8.2 ppm (—N H —), 8.9 (—O H )

Synthesis Example 10 Preparation of TIPTPAP (Compound (28)) Tris (phenylisocyanate) thiophosphate (TIPTP) in 27% by weight of ethyl acetate / chlorobenzene (70/3) (Death module RFE manufactured by Bayer, NCO equivalent: 581, nonvolatile content : 27% by weight) A solution obtained by adding 5 ml of DMAc to 11.62 g was slowly dropped into a DMAcml solution of 2.18 g (20 mmol, 1.0 equivalent) of AP using a dropping funnel, and the mixture was stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 4.44 g of a product. The structure was confirmed to be the formula (28) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 10.6%, the molecular weight was 792.2, and the factor (F) was 3.0.
IR: (cm ⁻¹ )
3331 cm ⁻¹ (O—H stretching vibration), 1652 cm ⁻¹ (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 6.4 to 7.6 ppm (Ph— H ), 8.3 to 8.7 ppm (—N H —), 9.1 (—O H )

Synthesis Example 11 Production of TDIHBA (Compound (23)) Using a dropping funnel, a solution obtained by adding 5 ml of DMAc to 8.90 g of TDI, 2.49 g (20 mmol, 1.mmol) of 4-hydroxybenzyl alcohol (HBA) (ACROS). 0 equivalent) of DMAc was slowly added dropwise to the solution and stirred at room temperature for 1 hour. The reaction solution was added to a large amount of water for crystallization, and the filtered crystal was dissolved in acetone, and then added to a large amount of water for crystallization to obtain a white powder. The obtained white powder was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 3/4. Finally, vacuum drying was performed to obtain 3.33 g of a product. The structure was confirmed to be the formula (23) by FT-IR and 400 MHz- ¹ H-NMR. The nitrogen content was 9.4%, the molecular weight was 894.3, and the factor (F) was 3.0.
IR: (cm ⁻¹ )
3355 (O—H stretching vibration), 1708 (C═O, carbonyl)
¹ H-NMR: (400 MHz, DMSO-d6, internal standard TMS)
δ (ppm): 7.0 to 8.3 (Ph— H ), 1.49 (—C (C H ₃ ) ₃ ), 2.1 to 2.4 (Ph—C H ₃ ), 3.34 (Ph—C H ₂ —O—), 9.1 (—N H —), 9.0 (—O H )

Examples 1-14
As shown in Table 1, the resist compound (A) (0.67 g) synthesized in Synthesis Examples 1 to 11, the acid generator (B) (0.01 g), the acid crosslinking agent (C) (0.33 g) A solvent (1.89 g) was added to the solution to obtain a homogeneous solution, followed by filtration through a Teflon (registered trademark) membrane filter having a pore size of 0.2 μm to prepare a resist solution. The obtained resist solution was spin-coated on the substrate shown in Table 2 to form a resist film. Table 2 shows the film formability of the obtained resist films.

Ａ−１：ＴＰＭＴＩＡＰ
Ａ−２：ＴＤＩＡＰ
Ａ−３：ＴＤＩＤＨＢＡ
Ａ−４：ＴＰＭＴＩＤＨＢＡ
Ａ−５：ＭＤＩＡＰ
Ａ−６：ＢＩＣＡＰ
Ａ−７：ＩＰＤＩＡＰ
Ａ−８：ＴＤＩＴＭＰＡＰ
Ａ−９：ＨＤＩＡＰ
Ａ−１０：ＴＩＰＴＰＡＰ
Ａ−１１：ＴＤＩＨＢＡ
Ｂ−１：１，２−ナフトキノン−２−ジアジド−５−スルホン酸ナトリウム（ＤＮＱ）
Ｃ−１：ニカラックＭＷ−１００ＬＭ（三和ケミカル（株）製）
Ｃ−２：ニカラックＮ−２７０２（三和ケミカル（株）製）
Ｃ−３：２,６−ビス（ヒドロキシメチル）−ｐ−クレゾール（関東化学（株）製）
ＰＧＭＥ；プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ；プロピレングリコールモノメチルエーテルアセテート

A-1: TPMTIAP
A-2: TDIAP
A-3: TDIDHBA
A-4: TPMTIDHBA
A-5: MDIAP
A-6: BICAP
A-7: IPDIAP
A-8: TDIMTPAP
A-9: HDIAP
A-10: TIPTPAP
A-11: TDIHBA
B-1: 1,2-naphthoquinone-2-diazide-5-sulfonic acid sodium salt (DNQ)
C-1: Nikarac MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)
C-2: Nicarak N-2702 (manufactured by Sanwa Chemical Co., Ltd.)
C-3: 2,6-bis (hydroxymethyl) -p-cresol (manufactured by Kanto Chemical Co., Inc.)
PGME; propylene glycol monomethyl ether PGMEA; propylene glycol monomethyl ether acetate

^＊表面処理剤：１，１，１，３，３，３−ヘキサメチルジシラザン

^* Surface treatment agent: 1,1,1,3,3,3-hexamethyldisilazane

Examples 15-28
After spin-coating the resist solutions prepared in Examples 1 to 14 on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven under the conditions shown in Table 3, and a resist film having a thickness of 0.2 μm. Formed. The resist film was exposed to i-line having a wavelength of 365 nm under the conditions shown in Table 3. Thereafter, the film was baked after exposure in an oven under the conditions described in Table 4, and developed at 23 ° C. by the standing method under the conditions described in Table 4. Thereafter, it was washed with water for 30 seconds and dried to form a negative resist pattern. The evaluation results are shown in Table 5.

  A scanning electron micrograph of the resist pattern obtained in Example 15 is shown in FIG. The dark part is the remaining resist in the unexposed part, and the thin part is the part where the resist is removed in the exposed part.

現像液：テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）２．３８ｗｔ％水溶液

Developer: Tetramethylammonium hydroxide (TMAH) 2.38 wt% aqueous solution

  In Examples 15 to 28, a 5 μmL & S pattern having a good pattern shape was obtained.

16 is a scanning electron micrograph showing the line pattern of the resist pattern obtained in Example 15. FIG.

Claims (26)

The following (a) to (d):
(A) The molecule has one or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group,
(B) the molecule has one or more substituents selected from the group consisting of a urea group, a urethane group, an amide group, and an imide group,
(C) molecular weight is 500-5000,
(D) A resist compound (A) having a branched structure that satisfies all the conditions, directly by irradiation with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, X-ray, and ion beam A resist composition comprising an acid generator (B) for generating an acid either indirectly or indirectly, and an acid crosslinking agent (C).   The resist composition according to claim 1, wherein the resist compound (A) has two or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, and an amino group in the molecule. The branched structure of the resist compound (A) has the following (1) to (4):
(1) having a tertiary carbon atom or a tertiary nitrogen atom not included in the cyclic structure,
(2) having a quaternary carbon atom,
(3) It contains at least one aromatic ring or aliphatic ring having 3 or more substituents.
(4) having a tertiary phosphorus atom,
(5) The resist composition according to claim 1 or 2, wherein the resist composition has a chemical structure satisfying at least one of the conditions including at least one isocyanurate ring. The resist compound (A) is
F ≦ 5
The resist composition according to any one of claims 1 to 3, which satisfies (F represents the total number of atoms / (total number of carbon atoms-total number of oxygen atoms)).   The resist composition according to claim 1, wherein the resist compound (A) has a phenolic hydroxyl group.   The resist compound (A) has at least one phenolic hydroxyl group in each molecular chain of the branched structure, and is composed of a urea bond, a urethane bond, an amide bond, and an imide bond in each molecular chain of the branched structure. The resist composition according to any one of claims 1 to 5, wherein the resist composition has one or more bond structures selected from the group.   The resist composition according to any one of claims 1 to 6, wherein the resist compound (A) has a nitrogen content of 1 to 30% by mass. The resist compound (A) is represented by the following formula (1):

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

Wherein at least three of X are of formula (I);
E represents a divalent acyclic hydrocarbon group having 1 to 12 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 12 carbon atoms, or a substituted alkylene group having 1 to 12 carbon atoms;
s, t, and u each independently represent an integer of 0 to 3, and a plurality of E, X, Z, and Y may be the same or different. )
A compound represented by
In the formula (I), R ¹ is a hydrogen atom or a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and A substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12 carbon atoms;
A represents hydrogen or a hydroxyl group, and at least one of A is a hydroxyl group;
Ar represents an aromatic hydrocarbon group having 6 to 12 carbon atoms;
Y represents 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 group 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 an integer of 1 to 5, and when n is an integer of 2 to 5, a plurality of R ¹ , A, Ar, a1, and r1 may be the same or different from each other. Item 8. The resist composition according to any one of Items 1 to 7. The compound of the formula (1) is represented by the formulas (4) to (6):

(In formulas (4) to (6), X and E are the same as above)
The resist composition according to claim 8, which is a compound represented by the formula: The resist compound (A) is represented by the following formula (2):

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

A group derived from any structure of
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)
A compound represented by
In the formulas (i) to (iii), R is a hydrogen atom, a linear hydrocarbon group having 1 to 12 carbon atoms, a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, And a substituent selected from the group consisting of 1-branched alkyl groups having 3 to 12 carbon atoms, wherein R ² is a hydrogen atom, a hydroxyl group, an acyclic hydrocarbon group having 1 to 12 carbon atoms, or a cyclic group having 3 to 12 carbon atoms. A hydrocarbon 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. Or a substituent selected from the group consisting of the groups: r, r is an integer from 0 to 4, k is an integer from 1 to 7, and a plurality of R and r may be the same. 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 carbon number. The resist composition according to any one of claims 1 to 7, wherein the resist composition represents a 3 to 12 divalent cyclic hydrocarbon group or a substituted alkylene group having 1 to 12 carbon atoms, and X is bonded to E '. Stuff. The compound of the formula (2) is represented by the following formula (9):

(In formula (9), X and R ² are the same as above)
The resist composition of Claim 10 which is a compound represented by these. The compound of the formula (2) is represented by the following formula (10):

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

(In formula (11), X and k are the same as above)
The resist composition according to claim 10, which is a compound represented by the formula: The compound of the formula (2) is represented by the following formula (12):

(In formula (12), X is as defined above)
The resist composition according to claim 10, which is a compound represented by the formula: The compound of the formula (2) is represented by the following formula (13):

(In formula (13), X is the same as above)
The resist composition according to claim 10, which is a compound represented by the formula: The compound of the formula (2) is represented by the following formula (14):

(In formula (14), X is as defined above)
The resist composition according to claim 10, which is a compound represented by the formula: The resist compound (A) is represented by the following formula (3):

(In 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 following formula (vi):

(In formula (vi), X and E ² are the same as above)
And E ¹ is a C 3-12 trivalent hydrocarbon group. 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 ² and J may be the same or different. The resist composition according to claim 1, wherein the resist composition is a compound represented by The compound of the formula (3) is 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 claim 17, which is a compound represented by the formula: The resist compound (A) is represented by the following formula (7):

(In formula (7), E ² , X and k are the same as above.)
The resist composition according to claim 1, which is a compound represented by the formula: X in each of the formulas (1) to (14) is the following formula (II) or (III):

(In formula (II) or (III), A is the same as described above, and m is an integer of 1 to 2)
The resist composition in any one of Claims 8-19 represented by these.   The resist composition according to claim 1, comprising two or more resist compounds (A).   The resist composition according to any one of claims 1 to 21, wherein the resist compound (A) is a compound that is dissolved in propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or ethyl lactate at 23% by weight or more at 23% by weight. The acid crosslinking agent (C) is represented by the following formulas (43) to (45):

(In the formulas (43) to (45), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 2 to 6 carbon atoms, and R ^{6 to} R ⁹ in the formula (43). Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxyl group having 1 to 5 carbon atoms, X ² represents a single bond, a methylene group, or an oxygen atom, and a plurality of R ⁵ , R ^{6 to} R ⁹ may be the same or different from each other)
The resist composition according to any one of claims 1 to 22, which is at least one compound selected from the group consisting of a compound represented by formula (1) and an alkoxymethylated melamine compound.   The resist composition (A) is 3 to 96.9% by weight, the acid generator (B) is 0.1 to 30% by weight, the acid crosslinking agent (C) is 3 to 65% by weight, and the total solid content of the resist composition is arbitrary. The resist composition according to any one of claims 1 to 23, comprising 0 to 93.9% by weight of component (D).   The resist composition (A) 65-96.9% by weight, acid generator (B) 0.1-30% by weight, acid crosslinking agent (C) 0.3-34.9%. The resist composition according to any one of claims 1 to 23, comprising 0% by weight and 0-30% by weight of an optional component (D).   The resist composition (A) 65-96.9 wt%, acid generator (B) 0.1-30 wt%, acid crosslinking agent (C) 0.6-30 wt% The resist composition according to any one of claims 1 to 23.

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