WO2012086370A1 - Photosensitive resin composition - Google Patents

Abstract

The present invention provides: an alkali-developable and negative-type photosensitive resin composition which exhibits excellent transparency, chemical resistance, heat resistance and alkali developability and which exhibits excellent heat resistance and long-term deterioration resistance requisite for a permanent resist and is suitable as an insulating layer; and a permanent resist using the photosensitive resin composition. Specifically, the present invention provides a photosensitive resin composition which comprises both a polysiloxane compound obtained by hydrolytic condensation among a specific unsaturated silane compound, a specific silane compound and a specific cyclic siloxane compound, and a photo radical generator.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition using a specific polysiloxane compound. More specifically, the present invention relates to an alkali developable negative photosensitive resin composition and a negative photoresist (especially permanent) using the photosensitive resin composition. Resist).

The negative type photoresist is a type of photoresist whose solubility in a developing solution is reduced by exposure and an exposed portion remains after development. Since conventional organic photoresists are used in negative photoresist developers, there is a problem in terms of environment, hygiene, and flammability. Organic solvents swell the photoresist during development, leading to fine wiring. This is difficult to cope with, and is not suitable for manufacturing a highly integrated semiconductor circuit. Therefore, development of a negative photoresist that can be developed with an alkaline solution such as tetramethylammonium hydroxide (TMAH) has been demanded.

On the other hand, a polysiloxane compound is a compound excellent in heat resistance, transparency, insulation and the like, and as an alkali developable negative photoresist, a blend of an acrylic polymer and epoxy polysiloxane (for example, Patent Document 1). And a resin composition based on a modified siloxane of an acrylic polymer (for example, see Patent Document 2) and the like are known. These conventional negative photoresists having a siloxane structure cannot be said to have sufficient chemical resistance such as acid resistance, alkali resistance, and solvent resistance, and further have insufficient heat resistance as a permanent resist. On the other hand, those having improved chemical resistance and heat resistance include diarylsilane diol, an alkoxysilane compound having an epoxy group or (meth) acryl group, and a polycondensation of an alkoxysilane having an acid anhydride structure. Although a resin composition containing siloxane as a base resin (for example, see Patent Document 3) is known, alkali developability is insufficient and a fine pattern cannot be formed.

JP-A-8-320564 JP 2008-201881 A JP 2009-19093 A

Accordingly, the object of the present invention is to have excellent transparency, chemical resistance, heat resistance and alkali developability, and further excellent heat resistance and aging resistance as a permanent resist, and an alkali developable negative suitable as an insulating layer. It is providing the permanent resist using the type photosensitive resin composition and this photosensitive resin composition.

As a result of intensive studies in view of the above, the present inventor has reached the present invention.
That is, the present invention provides a hydrolysis condensation reaction of an unsaturated silane compound represented by the following general formula (1), a silane compound represented by the following general formula (2), and a cyclic siloxane compound represented by the following general formula (3). It is the photosensitive resin composition containing the polysiloxane compound obtained by this, and a photoradical generator.

（式中、Ｒ¹は水素原子又はメチル基を表わし、Ｒ²は炭素数２～６の２価の飽和炭化水素基を表わし、Ｒ³は炭素数１～４のアルキル基を表わし、Ｘ¹は炭素数１～４のアルコキシ基又は塩素原子を表わし、ａは２又は３の数を表わす。）

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and X ¹ Represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and a represents a number of 2 or 3.

（式中、Ｒ⁴は同一でも異なってもよい炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、Ｘ²は炭素数１～４のアルコキシ基又は塩素原子を表わし、ｂは１又は２の数を表わす。）

Wherein R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, and X ² represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, b represents a number of 1 or 2.)

（式中、Ｒ⁵は炭素数１～４のアルキル基又は炭素数６～１０のアリール基を表わし、Ｘ³は下記一般式（４）で表わされる基又は下記一般式（５）で表わされる基を表わし、ｃは１分子あたりの下記一般式（４）で表わされる基の数である１～５の数を表わし、ｄは１分子あたりの下記一般式（５）で表わされる基の数である１～５の数を表わす。但し、ｃ＋ｄは３～６の数である。）

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ³ represents a group represented by the following general formula (4) or the following general formula (5). C represents a number of 1 to 5 which is the number of groups represented by the following general formula (4) per molecule, and d represents the number of groups represented by the following general formula (5) per molecule. Represents a number of 1 to 5, where c + d is a number of 3 to 6.)

（式中、Ｒ⁶は炭素数２～８の２価の炭化水素基を表わす。）

(Wherein R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms.)

（式中、Ｒ⁷は炭素数２～８の２価の脂肪族炭化水素基を表わし、Ｒ⁸及びＲ⁹は同一でも異なってもよい炭素数１～４のアルキル基を表わし、ｅは２又は３の数を表わす。）

(Wherein R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, R ⁸ and R ⁹ represent an alkyl group having 1 to 4 carbon atoms which may be the same or different, and e represents 2 Or represents a number of 3.)

The effect of the present invention is not only high transparency, but also excellent alkali developability, heat resistance that can withstand the temperature at the time of substrate production, chemical resistance such as acid resistance, alkali resistance, solvent resistance, and a permanent resist. The present invention provides an alkali-developable negative photosensitive resin composition excellent in heat resistance and aging resistance as an insulating layer, and a permanent resist and a method for producing the permanent resist using the photosensitive resin composition There is.

Hereinafter, the photosensitive resin composition and the permanent resist of the present invention will be described in detail based on preferred embodiments.

The photosensitive resin composition of the present invention comprises an unsaturated silane compound represented by the general formula (1), a silane compound represented by the general formula (2), and a cyclic siloxane compound represented by the general formula (3). It contains a polysiloxane compound (hereinafter also referred to as a polysiloxane compound of the present invention) obtained by a decomposition condensation reaction, and a photo radical generator. First, the polysiloxane compound of the present invention will be described.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a methyl group because of good storage stability. R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms. Examples of the divalent saturated hydrocarbon group having 2 to 6 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methylethylene, 2-methylethylene, 2-methylpropylene, 2 -Methylbutylene, 3-methylbutylene, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl and the like. As R ² , ethylene, propylene and butylene are preferable from the viewpoint of heat resistance of the cured product obtained from the photosensitive resin composition of the present invention and industrial availability of monomers as raw materials, and ethylene and propylene. Is more preferred, and propylene is most preferred.

In the general formula (1), R ³ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, t-butyl and the like. R ³ is preferably methyl, ethyl and propyl, more preferably methyl and ethyl, and most preferably methyl because hydrolysis reaction is easy and heat resistance is improved. X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, secondary butoxy, isobutoxy, t-butoxy and the like. X ¹ is preferably a methoxy, ethoxy and chlorine atom, more preferably methoxy and ethoxy, and most preferably methoxy because hydrolysis reaction is easy. a represents a number of 2 or 3. As a, since the heat resistance of the hardened | cured material obtained from the photosensitive resin composition of this invention improves, the number of 3 is preferable.

Of the unsaturated silane compounds represented by the general formula (1) in which a is a number 2, preferred compounds include (3-acryloxypropyl) methyldimethoxysilane and (3-acryloxypropyl) methyldiethoxysilane. , 3-acryloxypropyl) methyldichlorosilane, (3-acryloxypropyl) ethyldimethoxysilane, (3-acryloxypropyl) ethyldiethoxysilane, (3-acryloxypropyl) ethyldichlorosilane, (3-methacryloxy) Propyl) methyldimethoxysilane, (3-methacryloxypropyl) methyldiethoxysilane, (3-methacryloxypropyl) methyldichlorosilane, (3-methacryloxypropyl) ethyldimethoxysilane, (3-methacryloxypropyl) ethyldiethoxy Syrah , (3-methacryloxypropyl) ethyl dimethoxysilane, and (3-methacryloxypropyl) ethyldichlorosilane like.

Among the unsaturated silane compounds represented by the general formula (1) in which a is a number of 3, preferred compounds include (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) triethoxysilane, (3-acryloxypropyl) trichlorosilane, (3-methacryloxypropyl) trimethoxysilane, (3-methacryloxypropyl) triethoxysilane, (3-methacryloxypropyl) trichlorosilane and the like.

In the general formula (2), R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1). Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, Examples include tolyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl, phenethyl and the like. R ⁴ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably phenyl, because the heat resistance of the cured product obtained from the photosensitive resin composition of the present invention is improved. X ² represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include the alkoxy groups exemplified in the description of X ^{1 in} the general formula (1). X ² is preferably methoxy, ethoxy and a chlorine atom, more preferably methoxy and ethoxy, and most preferably methoxy because hydrolysis reaction is easy. b represents a number of 1 or 2. As b, the number of 2 is preferable because crack resistance is improved.

Although the silane compound represented by the general formula (2) may be used alone, b is a number of 1 because the heat resistance of the cured product obtained from the photosensitive resin composition of the present invention is improved. It is preferable to use a combination of a silane compound and a silane compound in which b is a number of 2. When a silane compound in which b is the number 1 and a silane compound in which b is the number 2 are used in combination, the silane compound in which b is the number 1 is compared with the silane compound in which b is the number 2. The molar ratio is preferably 0 to 10, more preferably 0.5 to 5, and most preferably 1 to 3. Further, silane compounds having different R ⁴ may be used in combination, but at least one of them is preferably a silane compound in which R ⁴ is phenyl. When silane compounds having different R ⁴ are used in combination, phenyl in R ⁴ is preferably 10 mol% or more, more preferably 20 mol% or more, and most preferably 30 mol% or more. .

Preferred examples of the silane compound represented by the general formula (2) in which b is the number 1 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrichlorosilane, ethyl Examples include trimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, and phenyltrichlorosilane.

Preferred examples of the silane compound represented by the general formula (2) in which b is a number of 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, diethyldimethoxysilane, and diethyl. Dietoxysilane, Diethyldichlorosilane, Methylphenyldimethoxysilane, Methylphenyldiethoxysilane, Methylphenyldichlorosilane, Ethylphenyldimethoxysilane, Ethylphenyldiethoxysilane, Ethylphenyldichlorosilane, Diphenyldimethoxy Examples include silane, diphenyldiethoxysilane, diphenyldichlorosilane, and the like.

In the general formula (3), R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1), and examples of the aryl group having 6 to 10 carbon atoms include those represented by the general formula (2). aryl groups such as exemplified in the description of R ⁴ are exemplified. R ⁵ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl, because of improved heat resistance.

In the general formula (3), X ³ represents a group represented by the general formula (4) or a group represented by the general formula (5). In the general formula (4), R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. Examples of the divalent hydrocarbon group having 2 to 8 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, 1-methylethylene, 2-methylethylene, 2-methylpropylene, 2- Divalent aliphatic hydrocarbon groups such as methylbutylene and 3-methylbutylene; divalent groups such as cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, 2-cyclohexylethane-1,4′-diyl And alicyclic hydrocarbon groups; divalent aromatic hydrocarbon groups such as 2-phenylethane-1,4′-diyl and the like. R ⁶ is ethylene, 2-methylethylene, and 2-phenyl from the viewpoint of the heat resistance of the cured product obtained from the photosensitive resin composition of the present invention and the industrial availability of the starting monomer. Ethane-1,4′-diyl is preferred, 2-methylethylene and 2-phenylethane-1,4′-diyl are more preferred, and 2-methylethylene is most preferred.

In the general formula (5), R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms. Examples of the divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms include the divalent aliphatic hydrocarbon groups exemplified in the description of R ^{6 in} the general formula (4). R ⁸ and R ⁹ represent the same or different alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{3 in} the general formula (1). R ⁸ and R ⁹ are preferably methyl and ethyl, and more preferably methyl, because the hydrolysis reaction is easy. e represents a number of 2 or 3. As e, since the reactivity is high, the number of 3 is preferable. c represents a number of 1 to 5 which is the number of groups represented by the general formula (4) per molecule, and d represents a number of groups represented by the general formula (5) of 1 to 5 per molecule. Represents the number 5. However, c + d is a number from 3 to 6. In view of industrial availability of raw materials, c + d is preferably a number of 3 to 5, more preferably a number of 3 to 4, and most preferably a number of 4.

The cyclic siloxane compound represented by the general formula (3) includes a compound represented by the following general formula (4a) and a compound represented by the following general formula (5a) on the SiH group of the compound represented by the following general formula (3a). Can be obtained by a hydrosilylation reaction.

（式中、Ｒ⁵、ｃ及びｄは上記一般式（３）と同義である。）

(In the formula, R ⁵ , c and d have the same meaning as in the general formula (3).)

（式中、Ｒ¹⁰はＳｉＨ基の水素原子と反応してＲ⁶となる不飽和基を表わす。）

(In the formula, R ¹⁰ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^6. )

（式中、Ｒ¹¹はＳｉＨ基の水素原子と反応してＲ⁷となる不飽和基を表わし、Ｒ⁸、Ｒ⁹及びｅは上記一般式（５）と同義である。）

(In the formula, R ¹¹ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^7, and R ⁸ , R ^9, and e have the same meaning as in the general formula (5).)

In the general formula (3a), R ⁵ , c and d have the same meaning as in the general formula (3). Preferred examples of the compound represented by the general formula (3a) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6, 8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10,12-hexa And methylcyclohexasiloxane.

In the general formula (4a), R ¹⁰ represents an unsaturated group that reacts with a hydrogen atom of a SiH group to become R ⁶ . Preferred examples of the compound represented by the general formula (4a) include acrylic acid, methacrylic acid, 3-methyl-3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7 -Octenoic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, 4-vinylcyclohexanecarboxylic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid and the like.

In the general formula (5a), R ¹¹ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^7, and R ⁸ , R ^9, and e have the same meaning as in the general formula (5). Among the compounds represented by the general formula (5a), preferable examples include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

The hydrosilylation reaction between the compound represented by the general formula (3a), the compound represented by the general formula (4a) and the compound represented by the general formula (5a) is a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based reaction. A catalyst such as a catalyst is preferably used, and a platinum-based catalyst is preferable because of good reactivity. Examples of platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite complexes (eg Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ), Dicarbonyldichloroplatinum and the like. From the viewpoint of reactivity, platinum-divinyltetramethyldisiloxane complex and platinum-carbonylvinylmethyl complex are preferable, Gold - carbonyl vinyl methyl complex is more preferable. The amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. preferable. The reaction conditions for the hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. Conventionally known solvents such as hexane, methyl isobutyl ketone, cyclopentanone and 1-methoxy-2-propyl acetate may be used.

When producing the cyclic siloxane compound represented by the general formula (3), hydrosilylation is performed using a compound capped with a protecting group instead of the compound represented by the general formula (4a), The protective group may be removed to form a cyclic siloxane compound represented by the general formula (3). Examples of the protecting group include tertiary alkyl groups such as t-butyl and t-pentyl; 1-alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, benzyloxymethyl, and 1-ethoxyethyl; trimethylsilyl, triethylsilyl, and the like. Alkylsilyl groups; alkoxycarbonyl groups such as t-butoxycarbonyl and t-pentyloxycarbonyl, and the like. Among these protecting groups, tertiary alkyl groups and alkoxymethyl groups are preferred, tertiary alkyl groups are more preferred, and t-butyl is preferred because industrial raw materials are easily available and elimination is easy. Is most preferred. For example, a compound in which the carboxyl group of the compound represented by the general formula (4a) is protected with t-butyl is a compound represented by the following general formula (4b).

（式中、Ｒ¹⁰はＳｉＨ基の水素原子と反応してＲ⁶となる不飽和基を表わす。）

(In the formula, R ¹⁰ represents an unsaturated group that reacts with a hydrogen atom of the SiH group to become R ^6. )

The t-butyl group of the protecting group is eliminated from the hydrosilylation reaction product of the compound represented by the general formula (3a), the compound represented by the general formula (4b), and the compound represented by the general formula (5a). Examples of the method include a method of desorbing boron trifluoride diethyl ether complex or the like in a solvent as a catalyst. Such solvents include alcohols such as methanol, ethanol, propanol, isopropanol; 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1- Ether alcohols such as methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2 And ether alcohol acetates such as -propyl acetate, 3-methoxy-1-butyl acetate and 3-methoxy-3-methyl-1-butyl acetate. The elimination of the protecting group may be after the hydrolysis condensation reaction with the unsaturated silane compound represented by the general formula (1) and the silane compound represented by the general formula (2).

In the reaction of the polysiloxane compound of the present invention, when the reaction ratio of the unsaturated silane compound represented by the general formula (1) is too small, curing is insufficient, and when it is too large, crack resistance is obtained. Is preferably 10 to 90% by mole, more preferably 20 to 75% by mole, and most preferably 25 to 65% by mole.

In the reaction of the polysiloxane compound of the present invention, when the reaction ratio of the silane compound represented by the general formula (2) is too small, curing is insufficient, and when it is too large, crack resistance is obtained. Is preferably 5 to 80% by mole, more preferably 10 to 70% by mole, and most preferably 15 to 60% by mole.

In the reaction of the polysiloxane compound of the present invention, when the reaction ratio of the cyclic siloxane compound represented by the general formula (3) is too small, the alkali developability becomes insufficient, and when the reaction ratio is too large, Since film loss during development increases, it is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and most preferably 15 to 70 mol%.

The hydrolysis condensation reaction of the unsaturated silane compound represented by the general formula (1), the silane compound represented by the general formula (2) and the cyclic siloxane compound represented by the general formula (3) is a so-called sol-gel reaction. Can be done. Examples of the sol-gel reaction include a method of performing a hydrolysis / condensation reaction in a solvent using a catalyst such as an acid or a base. The solvent used at this time is not particularly limited. For example, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, 1-methoxy-2-propanol acetate, 1,2-dimethoxyethane, toluene and the like can be mentioned. One of these can be used, or two or more can be mixed and used. Hydrolysis condensation reaction of alkoxysilane compounds and halosilane compounds is carried out by hydrolyzing alkoxysilyl groups and halosilyl groups with water to form silanol groups (Si-OH groups), and the generated silanol groups, silanol groups and alkoxysilyl groups. Or by the condensation of silanol and halosilyl group.

In order to rapidly advance this hydrolysis condensation reaction, it is preferable to add an appropriate amount of water, and the catalyst may be dissolved in water. The catalyst such as acid and base used in the hydrolysis condensation reaction may be any catalyst that promotes hydrolysis / condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid; formic acid, acetic acid, Organic acids such as oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; trimethylamine, Examples include amine compounds (organic bases) such as triethylamine, monoethanolamine, and diethanolamine. One of these may be used, or two or more may be used in combination. The temperature of the hydrolytic condensation reaction varies depending on the type of solvent, the type and amount of the catalyst, etc., but is preferably 0 to 80 ° C., more preferably 5 to 50 ° C., and most preferably 8 to 30 ° C.

In the polysiloxane compound of the present invention, silanol groups (SiOH groups) may remain due to its production method, but the storage stability of the photosensitive resin composition of the present invention may be reduced due to the presence of silanol groups. is there. For this reason, it may be sealed to inactivate the remaining silanol groups. Examples of the sealing method include trimethylsilylation with trichloromethylsilane, hexamethyldisilazane, etc., silanol esterification with a hydrolyzable ester, and the like. Examples of the hydrolyzable ester compound include orthoformate ester, orthoacetate ester, tetraalkoxymethane, carbonate ester and the like, and one or more of these may be used. In particular, orthoformic acid trialkyl ester, tetraalkoxymethane and the like are preferable.

Next, the photo radical generator will be described. In the present invention, the photo radical generator refers to a compound capable of initiating radical polymerization by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. As photo radical generators, since they are highly reactive and have little adverse effect on cured products, ketone compounds such as acetophenone compounds, diketone compounds, benzophenone compounds, thioxanthone compounds, and acylphosphine oxide compounds are used. preferable.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl. -2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azide Benzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -n- butyl ether, and benzoin isobutyl ether.

Examples of the diketone compound include diphenyl diketone, bis (4-methoxyphenyl) diketone, camphorquinone, 1,4-naphthoquinone, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, and 3,4-phenanthrenequinone. 9,10-phenanthrenequinone and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. It is done.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). -2,4,4-trimethylpentylphosphine oxide and the like.

The photo radical generator, which is a compound that initiates radical polymerization by irradiation with active energy rays, may be used alone or in combination of two or more.

Among the photo radical generators, acetophenone compounds are preferable from the viewpoint of curability, and 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- 1 is more preferable.

The preferred content of the photoradical generator in the photosensitive resin composition of the present invention varies depending on the type of photoradical generator, the wavelength and intensity of irradiation with active energy rays, etc., but 100 parts by mass of the polysiloxane compound of the present invention. On the other hand, the photoradical generator is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass. When the content of the photoradical generator is less than 0.05 parts by mass, the photosensitive resin composition of the present invention is not sufficiently cured, and when it is more than 10 parts by mass, an increase effect corresponding to the blending amount is obtained. In addition, it may adversely affect the physical properties of the cured product.

The photosensitive resin composition of the present invention may further contain an organic solvent. Examples of such organic solvents include aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene, and tetrahydronaphthalene; pentane, isopentane, hexane, isohexane, heptane, isoheptane, octane, isooctane. Saturated hydrocarbon compounds such as nonane, isononane, decane, isodecane, isododecane, cyclohexane, methylcyclohexane, menthane, decahydronaphthalene; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, Ether solvents such as 1,4-dioxane; acetone, methyl ethyl ketone, Ketone solvents such as ruisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, and cyclohexyl acetate; propylene glycol monomethyl ether acetate, ethylene glycol Examples thereof include glycol ester solvents such as monoethyl ether acetate, dipropylene glycol methyl ether acetate, and diethylene glycol monoethyl ether acetate. Among these organic solvents, ether solvents and glycol ether solvents are preferred, glycol ether solvents are more preferred, and propylene glycol monomethyl ether acetate is most preferred because of its excellent solubility and moderate evaporation rate. preferable. Moreover, these organic solvents may use only 1 type and may use 2 or more types together.

When the photosensitive resin composition of the present invention is used by a coating method or a printing method, the content of the organic solvent is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the polysiloxane compound of the present invention. More preferably, it is 10 to 100 parts by mass.

The photosensitive resin composition of the present invention preferably contains another polyfunctional acrylic compound because the mechanical strength of the cured product obtained from the photosensitive resin composition of the present invention is improved. In the present invention, the other polyfunctional acrylic compound refers to an acrylic compound having at least two acrylic groups or methacrylic groups other than the polysiloxane compound of the present invention. Examples of other polyfunctional acrylic compounds include ester acrylate compounds, epoxy acrylate compounds, urethane acrylate compounds, and the like.

The above ester acrylate compound is a compound obtained by condensing (meth) acrylic acid with an aliphatic alcohol or an aromatic hydroxy compound. Examples of such ester acrylate compounds include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, sorbitol hexa (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri Meth) acrylate.

The above-mentioned epoxy acrylate compound is a compound obtained by adding (meth) acrylic acid to an epoxy compound having an epoxy ring such as a glycidyl group or an alicyclic epoxy group. Examples of the epoxy compound used for such an epoxy acrylate compound include aromatic epoxy compounds such as phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether; trimethylolpropane polyglycidyl ether , Neopentyl diglycidyl ether, hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) tetramethylene glycol diglycidyl ether, and other aliphatic epoxy compounds; Heterocyclic structures such as nurate and triglycidyl tris (2-hydroxyethyl) isocyanurate 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl Cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl -3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopenta Diepoxide, ethylenebis (3,4-epoxycyclohexane carboxylate), alicyclic epoxy compounds such as 1,2-epoxy-2-epoxy ethyl cyclohexane. The epoxy acrylate compound can be obtained by adding (meth) acrylic acid or the like or a quaternary ammonium salt or the like to the above-mentioned epoxy compound as a catalyst.

The urethane acrylate compound is a compound obtained by reacting an isocyanate group of an isocyanate compound having at least two isocyanate groups with a hydroxyl group of an acrylic compound having a hydroxyl group such as hydroxymethyl (meth) acrylate or hydroxyethyl (meth) acrylate. Examples of the urethane compound used in such a urethane acrylate compound include aromatic isocyanate compounds such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate; Aliphatic isocyanate compounds such as diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; alicyclic isocyanate compounds such as isophorone diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate) Can be mentioned.

Among the other polyfunctional acrylic compounds described above, ester acrylate compounds and urethane acrylate compounds are preferred, and ester acrylate compounds are more preferred, since the effect of improving the mechanical strength of the cured product is great.

When the content of the other polyfunctional acrylic compound in the photosensitive resin composition of the present invention is too small, the effect of improving the mechanical strength of the cured product becomes insufficient, and when the content is too large, In addition to not being able to obtain an increase effect commensurate with the blending amount, it may adversely affect the heat resistance of the cured product, so that it is 5 to 250 parts by mass with respect to 100 parts by mass of the polysiloxane compound of the present invention. It is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight.

The photosensitive resin composition of the present invention preferably contains a polyfunctional epoxy compound because adhesion to the substrate is improved. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (glycol) (Dioxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane aliphatic epoxy compound; bisphenol A diglycidyl ether, bisphenol F di Aromatic epoxy resins such as glycidyl ether, phenol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds; 3,4-epoxy-6-methylcyclohexylmethyl-3,4- Alicyclic ring such as epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Epoxy compounds; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclo Examples thereof include pentadiene type epoxy compounds.

Among the polyfunctional epoxy compounds, an alicyclic epoxy compound and a heterocyclic epoxy compound are preferable, and a heterocyclic epoxy compound is more preferable because the effect of improving adhesion is large.

If the content of the polyfunctional epoxy compound in the photosensitive resin composition of the present invention is too small, the effect of improving the adhesion becomes insufficient, and if it is too large, the effect of increasing the amount corresponding to the blending amount. Is not preferable, and may adversely affect the physical properties of the cured product. Therefore, the amount is preferably 1 to 50 parts by weight, and preferably 30 to 30 parts by weight with respect to 100 parts by weight of the polysiloxane compound of the present invention. More preferred is 5 to 30 parts by mass.

In addition to the above, the photosensitive resin composition of the present invention, if necessary, a photosensitizer, a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, an antifoaming agent, a pigment, Optional components such as dyes can be blended.

In the photosensitive resin composition of the present invention, the amount of the optional component is preferably 400 parts by mass or less in total with respect to 100 parts by mass of the polysiloxane compound of the present invention.

The photosensitive resin composition of the present invention is cured by irradiating (exposing) active energy rays after forming a layer of the photosensitive resin composition of the present invention on an object such as a substrate. The method for forming the layer of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include dip coating, flow coating, brush coating, spray coating, extrusion coating, spin coating, and roll coating. For example, screen coating or roll transfer can be used to form a patterned film. The object on which the layer of the photosensitive resin composition of the present invention is formed is not particularly limited, and a silicon substrate, a glass substrate, a metal plate, a plastic plate, or the like is used depending on the application. The thickness of the layer of the photosensitive resin composition of the present invention formed on the object varies depending on the application, but when used for a permanent resist, 10 nm to 10 μm is a guide, and when used for an optical waveguide, The standard is 30-50 μm.

When the photosensitive resin composition of the present invention contains an organic solvent, after forming the layer of the photosensitive resin composition of the present invention, heat treatment (hereinafter also referred to as pre-baking) is performed for the purpose of removing the organic solvent in the layer. )I do. The conditions for the heat treatment are appropriately selected according to the boiling point and vapor pressure of the organic solvent used, the thickness of the layer of the photosensitive resin composition of the present invention, and the heat resistant temperature of the object on which the layer is formed. Heat treatment at ˜150 ° C. for 30 seconds to 10 minutes is a standard.

Examples of the case of irradiating the layer of the photosensitive resin composition of the present invention with active energy rays include ultrahigh pressure mercury lamps, deep UV lamps, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, and excimer lasers. It is appropriately selected according to the photosensitive wavelength of the radical generator or sensitizer. The irradiation energy of the active energy ray is appropriately selected depending on the layer thickness of the photosensitive resin composition, the type and amount of the photo radical generator.

Irradiation with active energy rays cures the photosensitive resin composition layer of the present invention, but heat treatment (hereinafter referred to as post-baking) is performed in order to improve the adhesion between the cured product layer and an object such as a substrate. May also be called). Such heat treatment is preferably performed at a temperature of 100 to 260 ° C. for 15 minutes to 2 hours in an inert gas atmosphere such as nitrogen, helium or argon.

The coating film obtained from the photosensitive resin composition of the present invention can be photolithography, and can be used as a negative photoresist. When the photosensitive resin composition of the present invention is used as a negative photoresist, the photosensitive resin composition of the present invention is exposed to active energy rays when irradiated to a coating film formed by applying the photosensitive resin composition to a substrate or the like. After coating the coating film of the photosensitive resin composition with a photomask and selectively irradiating active energy rays, the light-shielded part (uncured part) is dissolved and dispersed in an alkaline developer and removed (hereinafter referred to as development) In other words, a patterned cured film can be formed.

The alkali developer used for developing the coating film of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include inorganic alkalis such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium silicate, ammonia and the like. Primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; dimethylethanolamine; Tertiary alkanolamines such as methyldiethanolamine and triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5 Cyclic tertiary amines such as ene; aromatic tertiary amines such as pyridine, collidine, lutidine, and quinoline; alkaline aqueous solutions such as aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. The concentration can be the alkali concentration of the developer used for removing the conventional negative photosensitive resin composition layer. These alkaline aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant.

As a contact method with an alkaline aqueous solution, for example, any method such as a puddle method, a dipping method, a shower method, a spray method, etc. can be used, and the contact time is the molecular weight of the polysiloxane compound of the present invention, Although it depends on the temperature of the developer, etc., it is usually 30 to 180 seconds. After removing the portion having improved alkali solubility with an aqueous alkali solution, it is preferably rinsed with running water or water with a shower, and may be dehydrated and dried in the range of 50 to 120 ° C. if necessary.

The photosensitive resin composition of the present invention may be used by directly coating on an object such as a semiconductor substrate or the like, but it may be coated on a support film to form a coating film and used as a dry film resist. Good. The dry film resist is produced by pre-baking after forming a coating film to remove the solvent in the coating film, and laminating a protective film on the coating film surface. When using the dry film resist obtained from the photosensitive resin composition of the present invention, after peeling off the protective film from the dry film resist, the dry film resist is bonded to the object by thermocompression bonding, After peeling off the support film as necessary, exposure, development, and the like may be performed under the above conditions.
As the support film, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, and the like can be used, but a PET film is preferable because of excellent thermal characteristics and mechanical characteristics as the support film. The film thickness of the above support film is usually 1 μm to 5 mm, preferably 10 μm to 100 μm. The thickness of the coating film formed on the support film varies depending on the application and is not particularly limited, but is generally 0.1 μm to 100 μm, preferably 0.3 μm to 10 μm.

The cured film obtained from the photosensitive resin composition of the present invention is excellent in transparency, insulation, heat resistance, chemical resistance, and the like, and therefore for an active matrix substrate used in liquid crystal display devices, organic EL display devices, and the like. It is extremely useful as an interlayer insulating film, particularly an interlayer insulating film for an active matrix substrate having a TFT having a polycrystalline silicon thin film as an active layer. Further, it can be used for an interlayer insulating film of a semiconductor element. It can also be used for wafer coating materials (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating) and package materials (encapsulant, die bonding material) for semiconductor devices. .

The cured film obtained from the photosensitive resin composition of the present invention is also useful as an insulating film for semiconductor elements, multilayer wiring boards and the like. As semiconductor elements, individual semiconductor elements such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAM (dynamic random access memory), SRAM (static random access memory), EPROM (erasable programmable programmable) Theories of read-only memory (ROM), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), flash memory, etc., microprocessor, DSP, ASIC, etc. Circuit elements, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes, Such a photoelectric conversion element such as a load coupling device and the like. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass.

[Production Example 1: Production of polysiloxane compound A-1 of the present invention]
<Step 1: Production of cyclic siloxane compound a>
In a reaction vessel having a stirrer, a thermometer and a refluxer, 300 g of toluene as a solvent and 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a compound represented by the above general formula (3a) , And 0.0001 g of a platinum-divinyltetramethyldisiloxane complex (Karsttedt catalyst) was charged as a catalyst. While stirring, 213 g (1.5 mol) of methacrylic acid t-butyl ester as a compound represented by the above general formula (4b) was added over 1 hour at 60 ° C., and the mixture was further aged by stirring for 4 hours. Next, 77 g (0.52 mol) of vinyltrimethoxysilane was added as a compound represented by the general formula (5a) over 1 hour, and the mixture was further aged by stirring at 70 ° C. for 5 hours. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C., and the cyclic siloxane compound a (the carboxyl group in the above general formula (4) was capped (protected) with a t-butyl group was represented by the above general formula (3). Cyclic siloxane compound).

<Step 2: Production of polysiloxane compound A-1 of the present invention>
In a reaction vessel having a stirrer, a thermometer and a refluxer, 56.37 g (0.23 mol) of 3-methacryloxypropyltrimethoxysilane as a compound represented by the above general formula (1), As the compound represented, 123.35 g (0.15 mol) of the cyclic siloxane compound a, and as the compound represented by the general formula (2), 60 g (0.3 mol) of phenyltrimethoxysilane and 18.49 g (0 of diphenyldimethoxysilane) 0.08 mol) and 100 g of toluene as a solvent, and 30 g of 5% oxalic acid aqueous solution was added dropwise at 5 to 10 ° C. over 1 hour while cooling with ice, followed by further stirring at 10 ° C. for 15 hours. Reflux dehydration and dealcoholization treatment was performed at 50 ° C. under reduced pressure, and the solvent toluene was changed to propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) at 50 ° C. under reduced pressure to obtain a 25% PGMEA solution. In order to remove the t-butyl group, 5 g of boron trifluoride diethyl ether complex was added, and after stirring at 80 ° C. for 3 hours, an adsorbent for acidic substances (trade name: Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) 30 g was added and further stirred at 80 ° C. for 1 hour. The obtained slurry was filtered to remove solids and then concentrated under reduced pressure to obtain a 50% PGMEA solution of the polysiloxane compound A-1 of the present invention. The mass average molecular weight of the obtained polysiloxane compound A-1 of the present invention was determined by GPC analysis.

[Production Examples 2 and 3: Production of polysiloxane compounds A-2 and A-3 of the present invention]
The polysiloxane compound A-2 of the present invention was prepared in the same manner as in Production Example 1 except that the amount of the compounds represented by the general formulas (1) to (3) was changed to the number of moles shown in Table 1 below. A-3 in 50% PGMEA was obtained. The mass average molecular weights of the resulting polysiloxane compounds A-2 and A-3 of the present invention were determined by GPC analysis.

[Production Example 4: Production of polysiloxane compound A-4 of the present invention]
The silanol group of the polysiloxane compound A-1 of the present invention obtained in Production Example 1 was capped with a trimethylsilyl group by a conventional method using trimethylchlorosilane to prepare a 50% PGMEA solution of the polysiloxane compound A-4 of the present invention. Obtained. The mass average molecular weight of the obtained polysiloxane compound A-4 of the present invention was determined by GPC analysis.

In Table 1, for the polysiloxane compounds A-1 to A-4 of the present invention obtained in Production Examples 1 to 4, the number of moles of each compound used in the reaction (numbers in parentheses in Table 1), It described about the mass mean molecular weight by GPC analysis, and the state of the terminal group.

[Comparative Production Example 1: Production of Comparative Polysiloxane Compound A′-1]
In Production Example 1, instead of 123.35 g (0.15 mol) of cyclic siloxane compound a, 118.8 g (0.45 mol) of 2- (t-butoxycarbonyl) propyltrimethoxysilane was used and diphenyldimethoxysilane was used. The same procedure as in Production Example 1 was carried out except that the amount used was increased from 18.49 g (0.08 mol) to 36.5 g (0.15 mol), and 50 of the comparative polysiloxane compound A′-1 was used. A mass% PGMEA solution was obtained. The obtained comparative polysiloxane compound A′-1 had a mass average molecular weight of 3,200 as determined by GPC analysis.

[Comparative Production Example 2: Production of Comparative Polysiloxane Compound A′-2]
A 35 mass% PGMEA solution of a comparative polysiloxane compound A′-2 was obtained according to Synthesis Example 1 of JP-A-2008-201881. The obtained comparative polysiloxane compound A′-2 had a mass average molecular weight of 12,000 as determined by GPC analysis.

[Comparative Production Example 3: Production of Comparative Polysiloxane Compound A′-3]
According to Synthesis Example 1 of JP-A-2009-19093, in a reaction vessel having a stirrer, a thermometer and a refluxing vessel, 21.6 g (0.1 mol) of diphenylsilanediol, 3-methacryloxypropyltrimethoxysilane 11 0.7 g (0.05 mol), (3-triethoxysilylpropyl) succinic anhydride 15.2 g (0.05 mol) and tetra-isopropoxytitanium 0.63 g (2.2 mmol) as a catalyst were charged. While stirring, the temperature was gradually raised from room temperature to 80 ° C., and stirring was continued at 80 ° C. for 1 hour while refluxing the produced methanol. Thereafter, the mixture was cooled to 60 ° C., and the methanol and ethanol produced by gradually reducing the pressure were removed. After the degree of vacuum became 10 kPa or less, the mixture was stirred at 60 ° C. for 2 hours, so that the comparative polysiloxane compound A′- 3 was obtained.

[Examples 1 to 5 and Comparative Examples 1 to 5: Production and evaluation of the present invention and comparative photosensitive resin compositions]
Polysiloxane compounds A-1 to A-4 obtained in Production Examples 1 to 4, Comparative polysiloxane compounds A′-1 to A′-3 obtained in Comparative Production Examples 1 to 3, the following photo radical generators After blending with B-1 to B-3, the following organic solvents C-1 to C-3, and other polyfunctional acrylic compounds D-1 to D-3 as shown in Table 2 below, By filtration, photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared.

<Photoradical generator>
B-1: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1
B-2: 2,4-Diethylthioxanthone B-3: 2-Benzyl-2-dimethylamino-4′-morpholinobutyrophenone <Organic solvent>
C-1: PGMEA
C-2: Cyclohexanone C-3: N-methylpyrrolidone <Other polyfunctional acrylic compound>
D-1: Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate D-2: Dipentaerythritol hexaacrylate D-3: Polyethylene glycol (molecular weight 1000) dimethacrylate

For the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5, test pieces were prepared by the procedure described in [Preparation of test pieces] below, and the following evaluations were performed. The results are shown in Table 3.

(Preparation of test piece)
The photosensitive resin compositions of Examples 1 to 5 or Comparative Examples 1 to 5 were applied by spin coating on a 2.5 cm square glass substrate to form a coating film having a thickness of 2 μm after volatilization of the organic solvent. . This test piece was heat-treated at 100 ° C. for 6 minutes. A photomask having a line width of 10 μm was placed on the glass substrate after the heat treatment, and ultraviolet rays were irradiated at 200 mJ / cm ² with a high-pressure mercury lamp. Next, this test piece was immersed in a 0.4 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 30 seconds, washed with water to remove the alkali-soluble portion, and air-dried. Thereafter, heat treatment was performed at 230 ° C. for 1 hour in an air atmosphere to form a negative permanent resist, which was used as a test piece for the test. However, in the heat resistance test, a test piece was used which was subjected to the same operation as in the case of using a photomask except that ultraviolet rays were irradiated without using a photomask. In the present invention, the light transmittance means the light transmittance per 2 μm of film thickness at a wavelength of 400 nm, and the light transmittance before the test of the test pieces used in the following tests is 90% or more. there were. The film thickness was measured using a stylus type surface shape measuring instrument.

[Developability test]
The pattern on each test piece was observed with a scanning electron microscope, and developability was evaluated according to the following <Evaluation Criteria>. The residual film ratio means a film thickness ratio before and after development (100 × film thickness after development / film thickness before development).
<Evaluation criteria>
A: The pattern is formed well, the remaining film ratio is 90% or more, and the developability is excellent.
Δ: Residual film ratio is less than 90%, or a part of the pattern is broken, and developability is slightly inferior.
X: The pattern has many breaks or no pattern is formed, and the developability is poor.

[Acid resistance test]
Each test piece was immersed in a 5% by mass hydrochloric acid aqueous solution at 40 ° C. for 1 hour, and acid resistance was evaluated according to the following <Evaluation Criteria> based on the decrease rate of light transmittance before and after immersion.
<Evaluation criteria>
○: The reduction rate of light transmittance is less than 1%, and the acid resistance is excellent.
X: The reduction rate of light transmittance is less than 1%, and the acid resistance is poor.

[Alkali resistance test]
Each test piece was immersed in an alkali solution (monoethanolamine: N-methyl-2-pyrrolidone: butyl diglycol = 10: 30: 60 mass ratio) at 40 ° C. for 30 minutes, and the decrease rate of light transmittance before and after immersion. Thus, alkali resistance was evaluated according to the following <Evaluation Criteria>.
<Evaluation criteria>
○: The reduction rate of light transmittance is less than 1%, and the alkali resistance is excellent.
X: The reduction rate of the light transmittance is less than 1%, and the alkali resistance is poor.

[Solvent resistance test]
Each test piece was immersed in dimethyl sulfoxide at 80 ° C. for 1 hour, and the solvent resistance was evaluated according to the following <Evaluation Criteria> based on the decrease rate of light transmittance before and after immersion.
<Evaluation criteria>
○: The reduction rate of light transmittance is less than 1%, and the solvent resistance is excellent.
X: The reduction rate of light transmittance is less than 1%, and the solvent resistance is poor.

[Heat resistance test]
After heat-treating each test piece at 260 ° C. for 1 hour, the transmittance of light having a wavelength of 400 nm was measured, and the heat resistance was evaluated by the following <evaluation criteria>. The light transmittance in this test refers to the light transmittance per 2 μm of film thickness at a wavelength of 400 nm, and the light transmittance of each test piece before heat treatment at 260 ° C. is 95% or more. there were.
<Evaluation criteria>
A: The light transmittance is 95% or more, and the heat resistance is excellent.
X: Light transmittance is less than 95%, and heat resistance is poor.

From the results shown in Table 3, the photosensitive resin composition of the present invention using a polysiloxane compound having a specific structure is not only excellent in transparency but also insufficient in conventional negative photoresists having a siloxane structure. It was confirmed that it had excellent chemical resistance such as acid resistance, alkali resistance and solvent resistance, and further had heat resistance as a permanent resist.

Claims (4)

Polysiloxane compound obtained by hydrolytic condensation reaction of unsaturated silane compound represented by the following general formula (1), silane compound represented by the following general formula (2) and cyclic siloxane compound represented by the following general formula (3) And a photosensitive resin composition containing a photoradical generator.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and X ¹ Represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, and a represents a number of 2 or 3.

Wherein R ⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, and X ² represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom, b represents a number of 1 or 2.)

(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X ³ represents a group represented by the following general formula (4) or the following general formula (5). C represents a number of 1 to 5 which is the number of groups represented by the following general formula (4) per molecule, and d represents the number of groups represented by the following general formula (5) per molecule. Represents a number of 1 to 5, where c + d is a number of 3 to 6.)

(Wherein R ⁶ represents a divalent hydrocarbon group having 2 to 8 carbon atoms.)

(Wherein R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms, R ⁸ and R ⁹ represent an alkyl group having 1 to 4 carbon atoms which may be the same or different, and e represents 2 Or represents a number of 3.) The photosensitive resin composition according to claim 1, comprising another polyfunctional acrylic compound. The photosensitive resin composition of Claim 1 or 2 containing a polyfunctional epoxy compound. A permanent resist obtained from the photosensitive resin composition according to any one of claims 1 to 3.