KR20200063991A - Siloxane polymer containing isocyanuric acid and polyether skeletons, photosensitive resin composition, pattern forming process, and fabrication of opto-semiconductor device - Google Patents

Abstract

The present invention provides a novel polymer capable of implementing a high-transparent or high-light-resistant film, a photosensitive resin composition capable of forming a fine pattern with a wide range of wavelengths and implementing a high-transparent, high-light-resistant or high-heat-resistant film after forming the pattern, a method for forming a pattern using the corresponding photosensitive resin composition, and a method for preparing an optical semiconductor device. According to the present invention, there are provided a siloxane polymer comprising a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in a main chain and comprising an epoxy group in a side chain, and a photosensitive resin composition comprising the siloxane polymer and photo-acid generator.

Description

A siloxane polymer containing an isocyanuric acid skeleton and a polyether skeleton, a photosensitive resin composition, a method for forming a pattern, and a method for manufacturing an optical semiconductor device OF OPTO-SEMICONDUCTOR DEVICE}

The present invention relates to a siloxane polymer comprising an isocyanuric acid skeleton and a polyether skeleton, a photosensitive resin composition, a pattern forming method, and a method for manufacturing an optical semiconductor device.

Until now, epoxy resins have been mainly used as sealing protective materials in various optical devices represented by light emitting diodes (LEDs), CMOS image sensors, and the like. Among them, as a material having high transparency and light resistance, many epoxy-modified silicone resins have been used, and there is also a type in which an alicyclic epoxy group is introduced into the silphenylene skeleton (Patent Document 1).

In light resistance, even if there is no problem with a conventional device, since optical devices including LEDs in recent years have been undergoing high output, there has been a problem of gas generation and discoloration due to insufficient light resistance as a conventional sealing protection material. In addition, in recent years, various optical devices often require fine processing. In the case of performing such fine processing, various resist materials typified by epoxy resin-based materials have been used. However, the above-mentioned epoxy-modified silicone resin is not a material capable of fine processing of about 10 μm. As an epoxy resin applicable to the resist material, there is a type in which both terminal alicyclic epoxy-modified silphenylenes are introduced as a crosslinking agent (Patent Document 2), but when it is aimed at higher transparency, it is sufficient for heat resistance and light resistance. It was not possible, and a material capable of providing a film capable of withstanding even stricter conditions was desired.

Japanese Patent Publication No. Hei 8-32763 Japanese Patent Publication No. 2012-001668

The present invention has been made in view of the above circumstances, and a new polymer capable of imparting a high-transparency and high-light-resistant film, and capable of forming a fine pattern with a wide wavelength, while having high transparency, high light-resistance and high heat resistance after pattern formation An object of the present invention is to provide a photosensitive resin composition capable of imparting a coating, a pattern forming method using the photosensitive resin composition, and a method for manufacturing an optical semiconductor element.

The present inventors have repeatedly studied in order to achieve the above object. As a result, a polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric skeleton and a polyether skeleton in the main chain, and a polymer containing an epoxy group in the side chain are highly transparent. In addition, by providing a film with high light resistance and a photosensitive resin composition containing the polymer and a photo acid generator, fine patterns can be formed at a wide wavelength, and high transparency, high light resistance, and high heat resistance after pattern formation It was found that a film can be imparted, and the present invention was completed.

Accordingly, the present invention provides the following siloxane polymer, photosensitive resin composition, pattern forming method, and method for manufacturing an optical semiconductor device.

1. A siloxane polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain, and an epoxy group in the side chain.

2. The siloxane polymer of 1 wherein the transmittance of light having a wavelength of 405 nm of a film having a thickness of 10 μm including the polymer is 97% or more.

3. A siloxane polymer of 1 or 2 comprising repeating units represented by the following formulas (A1) to (A4).

[Wherein, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. m is an integer of 1 to 600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different from each other, and each R ⁴ may be the same or different from each other. a ¹ , a ² , a ³ and a ⁴ are 0<a ¹ <1, 0<a ² <1, 0<a ³ <1, 0<a ⁴ <1 and a ¹ +a ² +a ³ +a ^This is a number that satisfies ⁴ = 1. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2).

(In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group. n ¹ and n ² are each independently an integer of 0 to 7. R ¹³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, Ester bonds or ether bonds may be included between the carbon atoms.)

(Wherein, R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group. p ¹ and p ² are each Independently, it is an integer from 1 to 6. q is an integer from 0 to 100.)]

4. A siloxane polymer of 3 where q is an integer from 5 to 20.

5. A siloxane polymer of 3 or 4, where m is an integer from 10 to 100.

6. The siloxane polymer of any one of 3 to 5, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms.

7. The siloxane polymer of any one of 1 to 6 having a weight average molecular weight of 3,000 to 500,000.

8. A photosensitive resin composition comprising the siloxane polymer of any one of (A) 1 to 7 and (B) a photo acid generator.

9. The photosensitive resin composition of 8 whose content of (B) component is 0.05-20 mass parts with respect to 100 mass parts of (A) component.

10. Further, (C) 8 or 9 photosensitive resin composition containing a cationic polymerizable crosslinking agent.

11. Additionally, the photosensitive resin composition of any one of 8 to 10 comprising the (D) solvent.

12. Further, (E) the photosensitive resin composition of any one of 8 to 11 comprising an antioxidant.

13. (i) Process of forming photosensitive resin film on substrate using any one of 8 to 12 photosensitive resin composition,

(ii) the step of exposing the photosensitive resin film, and

(iii) Process of developing the exposed photosensitive resin film using a developer

Pattern formation method comprising a.

14. A method for manufacturing an optical semiconductor element comprising a photosensitive resin film, including the pattern forming method of 13.

The siloxane polymer of the present invention can be easily synthesized, and a high transparency and high light resistance film can be provided. In addition, by using the photosensitive resin composition containing the polymer and the photo acid generator, it is possible to easily form a film without being obstructed by oxygen, and the film can be exposed with light having a wide wavelength, thereby forming a fine pattern. Can form. Further, the coating obtained from the photosensitive resin composition of the present invention is excellent in transparency, light resistance and heat resistance, and can be suitably used for protection and sealing applications such as optical semiconductor elements.

[Siloxane polymer]

The siloxane polymer of the present invention includes a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain, and an epoxy group in the side chain.

As such a polymer, it is preferable to include repeating units represented by the following formulas (A1) to (A4) (hereinafter also referred to as repeating units A1 to A4, respectively).

In formulas (A2) and (A4), R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. m is an integer of 1 to 600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different from each other, and each R ⁴ may be the same or different from each other. When there are two or more siloxane units among the repeating units A2 and A4, each of the siloxane units may be the same or may contain two or more different siloxane units. When two or more different siloxane units are included (i.e., when m is an integer of 2 or more), the siloxane units may be randomly combined, alternately combined, or multiple blocks of the same type of siloxane units may be included. do.

The monovalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include monovalent aliphatic hydrocarbon groups such as alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. And monovalent aromatic hydrocarbon groups such as an aryl group and an aralkyl group having 7 to 20 carbon atoms.

As said alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclo Pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, norbornyl group, adamantyl group and the like. As said alkenyl group, vinyl group, propenyl group, butenyl group, pentenyl group, etc. are mentioned.

Further, the monovalent aliphatic hydrocarbon group may contain a hetero atom, and specifically, a part or all of the hydrogen atoms of the monovalent aliphatic hydrocarbon group are halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom. It may be substituted with the like, or a carbonyl group, an ether bond, a thioether bond, etc. may be interposed between the carbon atoms. A 2-oxocyclohexyl group etc. are mentioned as a monovalent aliphatic hydrocarbon group containing such a hetero atom.

As said aryl group, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethyl And phenyl groups, naphthyl groups, biphenylyl groups, and terphenylyl groups. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

Further, the monovalent aromatic hydrocarbon group may contain a hetero atom. Specifically, a part or all of the hydrogen atoms of the monovalent aromatic hydrocarbon group may be an alkoxy group having 1 to 10 carbon atoms or an alkyl tee having 1 to 10 carbon atoms. It may be substituted with an oligomer, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, or the like.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, cyclopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert -Butyloxy group, cyclobutyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, norbornyloxy group, adamantyloxy group, and the like.

Examples of the alkylthio group having 1 to 10 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, cyclopropylthio group, n-butylthio group, isobutylthio group, and sec-butylti. Ogi, tert-butylthio group, cyclobutylthio group, n-pentylthio group, cyclopentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, n-no Nylthio group, n-decylthio group, norbornylthio group, adamantylthio group, etc. are mentioned.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy group, 2-methylphenyloxy group, 3-methylphenyloxy group, 4-methylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, and 4-ethyl. And phenyloxy groups, 4-tert-butylphenyloxy groups, 4-butylphenyloxy groups, dimethylphenyloxy groups, naphthyloxy groups, biphenylyloxy groups, and terphenylyloxy groups.

Examples of the arylthio group having 6 to 20 carbon atoms include phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, 2-ethylphenylthio group, 3-ethylphenylthio group, and 4-ethyl. And phenylthio groups, 4-tert-butylphenylthio groups, 4-butylphenylthio groups, dimethylphenylthio groups, naphthylthio groups, biphenylylthio groups, and terphenylylthio groups.

For example, as the aryl group substituted with these groups, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 3- and tert-butoxyphenyl group, 4-tert-butoxyphenyl group, biphenylyloxyphenyl group, and biphenylylthiophenyl group.

As for the carbon number of the said monovalent aliphatic hydrocarbon group, 1-10 are preferable and 1-8 are more preferable. Moreover, 1-14 are preferable and, as for carbon number of the said monovalent aromatic hydrocarbon group, 1-10 are more preferable.

Of these, R ¹ to R ⁴ are preferably a methyl group, an ethyl group, an n-propyl group or a phenyl group, and more preferably a methyl group or a phenyl group.

In formulas (A2) and (A4), m is an integer of 1 to 600 each independently, but an integer of 8 to 100 is preferred.

In formulas (A1) to (A4), a ¹ , a ² , a ³ and a ⁴ are 0<a ¹ <1, 0<a ² <1, 0<a ³ <1, 0<a ⁴ <1 and This is a number that satisfies a ¹ +a ² +a ³ +a ⁴ =1. Preferably, 0.010≤a ¹ +a ² ≤0.490, 0.010≤a ³ +a ⁴ ≤0.490, 0.050≤a ¹ +a ³ ≤0.490, 0.010≤a ² +a ⁴ ≤0.450 and a ¹ +a ² + a ³ +a ⁴ =1, more preferably, 0.050≤a ¹ +a ² ≤0.450, 0.050≤a ³ +a ⁴ ≤0.450, 0.200≤a ¹ +a ³ ≤0.450, 0.050≤ It is a number that satisfies a ² +a ⁴ ≤0.300 and a ¹ +a ² +a ³ +a ⁴ =1.

In formulas (A1) and (A2), X ¹ is a divalent group represented by the following formula (X1).

In formula (X1), R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group. n ¹ and n ² are each independently an integer of 0 to 7.

In Formula (X1), R ¹³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and may contain an ester bond or an ether bond between the carbon atoms. The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, and propane-1,2-. And alkanediyl groups such as diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, and butane-1,4-diyl group. Further, an ester bond or an ether bond may be interposed between the carbon atoms of the divalent hydrocarbon group. Among them, as R ¹³ , a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

In formulas (A3) and (A4), X ² is a divalent group represented by the following formula (X2).

In formula (X2), R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group. p ¹ and p ² are each independently an integer of 1 to 6, but an integer of 1 to 4 is preferable, and 1 or 2 is more preferable. q is an integer from 0 to 100, but an integer from 1 to 50 is preferable, and an integer from 5 to 20 is more preferable.

The monovalent hydrocarbon group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include monovalent aliphatic hydrocarbon groups such as an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms, And monovalent aromatic hydrocarbon groups such as an aryl group having 6 to 8 carbon atoms and an aralkyl group having 7 or 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n -Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like. As said alkenyl group, vinyl group, propenyl group, butenyl group, pentenyl group, etc. are mentioned.

As said aryl group, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, dimethylphenyl group, etc. are mentioned. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

As R ²¹ and R ²² , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.

In the formula (X2), the alkylene oxide units represented by the subscript q may be randomly bonded or alternately bonded, or may contain a plurality of blocks of the same type of alkylene oxide units.

The siloxane polymer of the present invention preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. If Mw is in the above range, a polymer can be obtained as a solid, and also film-forming properties can be secured. In addition, in this invention, Mw is the measured value of polystyrene conversion by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

The siloxane polymer of the present invention may be one in which the repeating units A1 to A4 are randomly combined, or may be alternately bonded, or may contain a plurality of blocks of each unit. Moreover, in the siloxane polymer of this invention, it is preferable that the content rate of a siloxane unit is 10 to 90 mass %.

[Method for producing siloxane polymer]

The siloxane polymer of the present invention is a compound represented by the following formula (1) (hereinafter also referred to as compound (1)) and a compound represented by the following formula (2) (hereinafter also referred to as compound (2)) and , A compound represented by the following formula (3) (hereinafter also referred to as compound (3)) and a compound represented by the following formula (4) (hereinafter also referred to as compound (4)) in the presence of a metal catalyst, It can be produced by addition polymerization.

(In the formula, R ¹ to R ⁴ , R ¹¹ to R ¹³ , R ²¹ to R ²⁴ , m, n ¹ , n ² , p ¹ , p ² and q are the same as above.)

Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; H ₂ PtCl ₄ ·xH ₂ O, H ₂ PtCl ₆ ·xH ₂ O, NaHPtCl ₆ ·xH ₂ O, KHPtCl ₆ ·xH ₂ O, Na ₂ PtCl ₆ ·xH ₂ O, K ₂ PtCl ₄ ·xH ₂ O, PtCl ₄ ·xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ ·xH ₂ O (where x is an integer from 0 to 6 is preferred, especially 0 or 6), such as platinum chloride, chloroplatinic acid and chloride Platinum salts; Alcohol-modified chloroplatinic acid (eg, as described in US Pat. No. 3,220,972); Complexes of chloroplatinic acid with olefins (eg, those described in US Pat. No. 3,159,601, US Pat. No. 3,159,662, and US Pat. No. 3,775,452); A platinum group metal such as platinum black or palladium supported on a carrier such as alumina, silica or carbon; Rhodium-olefin complex; Chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); And a complex of platinum chloride, chloroplatinic acid or chloroplatinic acid salt and vinyl group-containing siloxane (especially vinyl group-containing cyclic siloxane).

The amount of the catalyst used is the amount of the catalyst, and it is usually 0.001 to 0.1% by mass as the platinum group metal among the total mass of the compounds (1) to (4).

In the said polymerization reaction, you may use a solvent as needed. As the solvent, for example, hydrocarbon-based solvents such as toluene and xylene are preferable. As the polymerization conditions, from the viewpoint that the catalyst is not deactivated and polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150°C, particularly 60 to 120°C, for example. Although the polymerization time varies depending on the type and amount of the raw material compound, it is preferable to end at about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent the intervention of moisture in the polymerization system. When the polymerization reaction is completed in this way and a solvent is used, the polymer can be obtained by distilling it off.

Although the reaction method is not particularly limited, first, compound (3) and compound (4) are mixed and heated, then a metal catalyst is added to the mixed solution, and then compound (1) and compound (2) are added in an amount of 0.1 to Dropping over 5 hours is recommended.

Each raw material compound has a molar ratio, preferably 0.67 to 1.67, more preferably, the hydrosilyl group of the compound (1) and the compound (2) with respect to the sum of the alkenyl groups of the compound (3) and the compound (4). It is good to blend so that it becomes 0.83 to 1.25. The Mw of the siloxane polymer of the present invention can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrosilane such as triethylhydrosilane or monohydrosiloxane as a molecular weight modifier.

[Photosensitive resin composition]

The photosensitive resin composition of this invention contains (A) the above-mentioned siloxane polymer and (B) photo acid generator. (A) The siloxane polymer of a component may be used individually by 1 type and may use 2 or more types together.

[(B) Light acid generator]

The photo acid generator of the component (B) is not particularly limited as long as it is decomposed by light irradiation to generate an acid, but it is preferable to generate an acid by irradiating light having a wavelength of 190 to 500 nm. (B) The photo acid generator is used as a curing catalyst. Examples of the photo acid generator include onium salt, diazomethane derivative, glyoxime derivative, β-ketosulfone derivative, disulfone derivative, nitrobenzylsulfonate derivative, sulfonic acid ester derivative, imide-yl-sulfonate And derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

As said onium salt, the sulfonium salt represented by following formula (B1) or the iodonium salt represented by following formula (B2) is mentioned.

In formulas (B1) and (B2), R ¹⁰¹ to R ¹⁰⁵ may each independently have a C1-C12 alkyl group which may have a substituent, a C6-C12 aryl group which may have a substituent, or a substituent. It is an aralkyl group having 7 to 12 carbon atoms. A ^- is a non-nucleophilic counterion.

The alkyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl Group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like. A phenyl group, a naphthyl group, a biphenylyl group, etc. are mentioned as said aryl group. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

Examples of the substituent include an oxo group, a straight-chain, branched or cyclic alkoxy group having 1 to 12 carbon atoms, a straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, and 7 to 25 carbon atoms. And an aralkyl group, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms, and the like.

Examples of R ¹⁰¹ to R ¹⁰⁵ include alkyl groups which may have substituents such as methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, norbornyl group, adamantyl group, and 2-oxocyclohexyl group; Phenyl group, naphthyl group, biphenylyl group, o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group, 2-, 3- or 4-methylphenyl group, ethylphenyl group, An aryl group which may have a substituent such as 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, terphenylyl group, biphenylyloxyphenyl group, or biphenylylthiophenyl group; An aralkyl group which may have a substituent such as a benzyl group or a phenethyl group is preferable. Among these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are more preferable.

Examples of the non-nucleophilic counter ion include halide ions such as chloride ions and bromide ions; Fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; Arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate ion; Alkanesulfonate ions such as mesylate ion and butanesulfonate ion; Fluoroalkane sulfonimide ions such as trifluoromethane sulfonimide ion; Fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; And borate ions such as tetrakisphenyl borate ion and tetrakis(pentafluorophenyl) borate ion.

As said diazomethane derivative, the compound represented by following formula (B3) is mentioned.

In formula (B3), R ¹¹¹ and R ¹¹² are each independently an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group include the same ones exemplified in the explanation of R ¹⁰¹ to R ¹⁰⁵ . Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group.

Examples of the aryl group which may have the substituent include a phenyl group; Alkoxyphenyl groups such as 2-, 3- or 4-methoxyphenyl groups, 2-, 3- or 4-ethoxyphenyl groups, and 3- or 4-tert-butoxyphenyl groups; Alkyl phenyl groups such as 2-, 3- or 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, and dimethylphenyl group; And halogenated aryl groups such as fluorophenyl group, chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group and the like. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

As said glyoxime derivative, the compound represented by following formula (B4) is mentioned.

In formula (B4), R ¹²¹ to R ¹²⁴ are each independently an alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. In addition, R ¹²³ and R ¹²⁴ may be bonded to each other to form a ring together with the carbon atom to which they are attached, and when forming a ring, groups formed by bonding of R ¹²³ and R ¹²⁴ are groups having 1 to 12 carbon atoms. It is a chain or branched alkylene group.

As said alkyl group, a halogenated alkyl group, the aryl group which may have a substituent, and an aralkyl group, the thing similar to what was illustrated as R ¹¹¹ and R ¹¹² is mentioned. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

Specifically as the onium salt, diphenyl iodonium trifluoromethanesulfonic acid, trifluoromethanesulfonic acid (p-tert-butoxyphenyl)phenyl iodonium, p-toluenesulfonic acid diphenyl iodonium, p- Toluenesulfonic acid (p-tert-butoxyphenyl)phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl)diphenylsulfonium, trifluoromethanesulfonic acid Bis(p-tert-butoxyphenyl)phenylsulfonium, trifluoromethanesulfonic acid tris(p-tert-butoxyphenyl)sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert- Butoxyphenyl)diphenylsulfonium, p-toluenesulfonic acid bis(p-tert-butoxyphenyl)phenylsulfonium, p-toluenesulfonic acid tris(p-tert-butoxyphenyl)sulfonium, nonafluorobutanesulfonic acid tri Phenylsulfonium, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate(2-oxocyclohexyl)sulfonium, p-toluenesulfonate Cyclohexylmethyl(2-oxocyclohexyl)sulfonium, dimethylphenylsulfonium trifluoromethanesulfonic acid, dimethylphenylsulfonium p-toluenesulfonic acid, dicyclohexyl trifluoromethanesulfonic acidphenylsulfonium, dicyclo p-toluenesulfonate Hexylphenylsulfonium, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenyl Rylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, tetrakis(fluorophenyl)borate triphenylsulfonium, tetrakis(fluorophenyl)triborate [4 -(4-acetylphenyl)thiophenyl]sulfonium, tetrakis(pentafluorophenyl)triphenylsulfonium borate, tetrakis(pentafluorophenyl)tris triborate [4-(4-acetylphenyl)thiophenyl]sul And phonium.

Specifically as the diazomethane derivative, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)dia Crude methane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis (n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isophene) Tilsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane , 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

Specifically as the glyoxime derivative, bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o- (p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl -3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o -(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)- 2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis- o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctane Sulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p- Fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, And bis-o-(camposulfonyl)-α-dimethylglyoxime.

Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like. have.

Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

Specific examples of the nitrobenzyl sulfonate derivatives include p-toluene sulfonic acid 2,6-dinitrobenzyl, p-toluene sulfonic acid 2,4-dinitrobenzyl, and the like.

Specifically as the sulfonic acid ester derivative, 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris( and p-toluenesulfonyloxy)benzene.

Specifically as the imide-yl-sulfonate derivative, phthalimide-yl-triflate, phthalimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-triflate , 5-norbornene-2,3-dicarboxyimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-n-butylsulfonate, n-trifluoromethylsulfonyl And oxynaphthylimide.

Specific examples of the oxime sulfonate derivatives include α-(benzenesulfoniumoxyimino)-4-methylphenylacetonitrile and the like.

Specifically as the iminosulfonate derivative, (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-( 4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile and the like.

Further, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be suitably used.

As the photo acid generator of the component (B), the onium salt is particularly preferable, and the sulfonium salt is more preferable.

The content of the component (B) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the component (A). When the content of the component (B) is within the above range, sufficient photocurability is easily obtained, and further, it is possible to effectively prevent deterioration of curability in the thick film due to light absorption of the photoacid generator itself. In addition, in order to obtain transparency and light resistance, which are the characteristics of the present invention, the blending amount of the photoacid generator of the component (B) having light absorption is preferably less in a range that does not impair the photocurability. (B) The photo acid generator of a component may be used individually by 1 type and may use 2 or more types together.

[(C) Cationic polymerizable crosslinking agent]

The photosensitive resin composition of the present invention may further contain a cationic polymerizable crosslinking agent as the component (C). The cationic polymerizable crosslinking agent is capable of causing a cationic polymerization reaction with the epoxy group of the component (A), and is a component that can easily form a pattern, and further increases the strength of the resin film after photocuring.

As the crosslinking agent, a compound having a molecular weight of 100 to 15,000 is preferable, and a compound of 200 to 1,000 is more preferable. If the molecular weight is 100 or more, sufficient photocurability can be obtained, and if it is 15,000 or less, it is preferable because there is no fear of deteriorating the heat resistance after photocuring of the composition. Further, the compound may be a resin (polymer), and in this case, the molecular weight is a weight average molecular weight (Mw).

As the cationic polymerizable crosslinking agent, a compound having a functional group selected from an epoxy group, an oxetane group and a vinyl ether group is preferable. You may use these compounds individually by 1 type or in combination of 2 or more type.

(C) Content of component is 0-100 mass parts with respect to 100 mass parts of (A) component, but when it contains, 0.5-100 mass parts is preferable, 0.5-60 mass parts is more preferable, 1-50 mass parts Addition is more preferred. When the content of the component (C) is 0.5 parts by mass or more, sufficient curing property is obtained upon irradiation with light, and when the content of the component (A) is 100 parts by mass or less, the proportion of the component (A) in the photosensitive resin composition does not decrease. Effect can be expressed. (C) A component can be used individually by 1 type or in combination of 2 or more type.

[(D) Solvent]

The photosensitive resin composition of this invention may contain a solvent as (D) component in order to improve the coating property. (D) The solvent is not particularly limited as long as it is capable of dissolving the above-mentioned components (A) to (C) and the components (E) and other various additives described later.

(D) As the solvent, an organic solvent is preferable, and specific examples thereof include ketones such as cyclohexanone, cyclopentanone and methyl-2-n-pentyl ketone; Alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; Ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropionate methyl, 3-ethoxypropionate ethyl, tert-butyl acetate, tert-butyl propionate, propylene glycol- And esters such as mono-tert-butyl ether acetate and γ-butyrolactone. These may be used alone or in combination of two or more.

As the (D) solvent, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof are particularly preferred, which are excellent in solubility of the photo acid generator.

When (D) component is included, the content is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, based on 100 parts by mass of component (A), from the viewpoint of compatibility and viscosity of the photosensitive resin composition. , 50 to 100 parts by mass is more preferable.

[(E) Antioxidant]

The photosensitive resin composition of the present invention may contain an antioxidant as an additive. Heat resistance can be improved by including an antioxidant. As said antioxidant, a hindered phenol type compound, a hindered amine type compound, etc. are mentioned.

Although it does not specifically limit as said hindered phenol type compound, It is preferable to be listed below. For example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di- tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (Brand name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (brand name: Nocrac DAH), 2,2'-methylene bis (4-methyl-6-tert-butylphenol) (brand name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert -Butylphenol) (trade name: Nocrac 300), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylidene bis (3 -Methyl-6-tert-butylphenol) (trade name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl Acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (brand name: Sinox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert- Butylphenyl) butane (trade name: Adekastab AO-30), tetrakis [methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane (trade name: Adekastab AO-60 ), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)prop Lopionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5 -Triazine (trade name: IRGANOX 565), N,N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexane Diol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis[3-(3,5 -Di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) )Propionyloxy] 1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl- 4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium/polyethylene wax mixture (50:50) (brand name) : IRGANOX 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1135), 4,4'-thiobis (6-tert-butyl -3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra- tert-butyldibenz[d,f][1,3,2]dioxaphosphine (trade name: Sumilizer GP); and the like.

Although it does not specifically limit as said hindered amine type compound, It is preferable to be listed below. For example, p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydro Quinoline) (trade name: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p- Phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine ( Trade names: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (brand name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (brand name: Nocrac CD), p ,p-Toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacrylyloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1) , N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl-1- succinate (2-hydroxyethyl)- 4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly [[6-(1,1,3,3-tetramethylbutyl)amino-1,3 ,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4 -Piperidyl)imino]] (brand name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2, 6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl -4-piperidyl) sebacate (trade name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2 ,6,6-pentamethyl-4-piperidyl) (trade name: TINUVIN 144), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: TINUVIN 765) , Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2) ,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), 1,2,3,4-butanetetracarboxylic acid and 1, Mixed esterified product of 2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), 1,2,3,4-butanetetracarboxylic acid and 2,2 Mixed esterified product of 6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2,3,4-butanetetracarboxylic acid and 1,2,2, Mixing of 6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane Esterified products (trade name: LA-63P), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy Mixed esterified product of -1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4 -Piperidyl)-2-propylenecarboxylate (trade name: Adekast LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylenecarboxylate (Brand name: Adeka staff LA-87) and the like.

The content of the component (E) is not particularly limited as long as the effects of the present invention are not impaired, but when contained, 0.01 to 1% by mass is preferable in the photosensitive resin composition of the present invention. (E) Antioxidant of component may be used individually by 1 type and may use 2 or more types together.

[Other additives]

The photosensitive resin composition of this invention may contain other additives other than each component mentioned above. Examples of the additives include surfactants commonly used to improve coating properties.

The surfactant is preferably a nonionic one, for example, a fluorine-based surfactant, specifically perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, or fluorine-containing organosiloxane system And compounds. As these, commercially available ones can be used, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M), Sufflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.) , Unidime (registered trademark) DS-401, DS-4031 and DS-451 (manufactured by Daikin High School), Megapak (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 (Made by Shin-Etsu Chemical Co., Ltd.) and the like. Among these, Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is not particularly limited as long as the effects of the present invention are not impaired, but when contained, 0.01 to 1% by mass is preferable in the photosensitive resin composition of the present invention.

Moreover, a silane coupling agent can also be used as an additive. By containing a silane coupling agent, the adhesiveness of the photosensitive resin composition to an adherend can be further improved. Examples of the silane coupling agent include an epoxy silane coupling agent and an aromatic-containing aminosilane coupling agent. These can be used individually by 1 type or in combination of 2 or more type. The content of the silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but when contained, 0.01 to 5% by mass is preferable in the photosensitive resin composition of the present invention.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include a method of stirring and mixing the above components, and then filtering with a filter or the like to remove solids as necessary.

[Pattern formation method]

The pattern forming method of the present invention is to use the photosensitive resin composition,

(i) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above,

(ii) the step of exposing the photosensitive resin film, and

(iii) Process of developing the exposed photosensitive resin film using a developer

It is to include. A fine pattern can be obtained by this method.

Step (i) is a step of forming a photosensitive resin film on the substrate using the photosensitive resin composition. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, and ceramic circuit boards.

The photosensitive resin film can be formed by a known method. For example, it can be formed by applying the photosensitive resin composition on a substrate by a method such as an immersion method, a spin coating method, or a roll coating method. Although the coating amount can be appropriately selected depending on the purpose, an amount such that the film thickness is 0.1 to 100 µm is preferable.

Here, in order to perform the photocuring reaction efficiently, a solvent or the like may be evaporated in advance by preliminary heating as necessary. Preliminary heating can be performed, for example, at 40 to 160°C for about 1 minute to 1 hour.

Subsequently, as the step (ii), the photosensitive resin film is exposed. At this time, it is preferable to expose with light having a wavelength of 240 to 500 nm. Examples of the light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generating device, for example, ultraviolet rays such as g-rays and i-rays, and far-infrared rays (248 nm). The exposure amount is preferably 10 to 5,000 mJ/cm 2.

Exposure may be performed through a photomask. The photomask may be, for example, a cutout of a desired pattern. Further, the material of the photomask is preferably to shield the light having the wavelength of 240 to 500 nm, for example, chromium or the like is suitably used, but is not limited to this.

Further, in order to increase the development sensitivity, a heat treatment (PEB) may be performed after exposure. PEB can be made, for example, at 40 to 160°C for 5 to 30 minutes.

Step (iii) is a step of developing the photosensitive resin film after exposure or after PEB using a developer. As the developer, organic solvent-based developer used as a solvent, for example, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferable. By developing using the organic solvent-based developer, a negative pattern obtained by dissolving and removing the non-exposed portion is obtained. The development can be performed by a conventional method, for example, by immersing a substrate on which a pattern is formed, in the developer. Then, if necessary, washing, rinsing, drying, and the like are performed to obtain a coating having a desired pattern.

The method for forming a pattern is as described above, but when it is not necessary to form a pattern, for example, to form a simple uniform film, in step (ii) in the pattern forming method, the The film may be formed by exposure to light of an appropriate wavelength without passing through a photomask.

In addition, if necessary, (iv) heating the film formed with a pattern at 120 to 300° C. for 10 minutes to 10 hours using an oven or a hot plate to increase crosslink density and remove residual volatile components. Treatment (post-curing) may be performed.

[Optical semiconductor device]

By forming a fine pattern by the above method using the photosensitive resin composition, an optical semiconductor element can be manufactured. In addition, the coating obtained from the photosensitive resin composition is excellent in transparency, light resistance and heat resistance, and the optical semiconductor device provided with the coating includes light-emitting elements such as light-emitting diodes, photodiodes, optical sensors, and CMOS image sensors. , It is suitably used for optical devices such as optical transmission devices such as optical waveguides. It is preferable that the transmittance|permeability of the light of wavelength 405 nm is 92% or more, it is more preferable that it is 96% or more, and it is especially preferable that it is 98% or more.

[Example]

Hereinafter, the present invention will be further described by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following Examples, Mw is a GPC column using TSKGEL Super HZM-H (manufactured by Tosoh Co., Ltd.), under the analysis conditions of a flow rate of 0.6 mL/min, an elution solvent THF, and a column temperature of 40°C. Dispersion polystyrene was measured by GPC as a standard.

Compounds (S-1), (S-2a), (S-2b), (S-3a), (S-3b), (S-4), (S-5) and (S) used for the synthesis of polymers -6) is as follows.

[1] Synthesis of polymers and evaluation thereof

(1) Synthesis of polymer

[Example 1-1] Synthesis of Polymer 1

After adding 132.5 g (0.50 mol) of compound (S-4) and 269.5 g (0.50 mol) of compound (S-3a) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. It was added and heated to 70°C. Thereafter, 1.0 g of toluene chloride solution (platinum concentration 0.5 mass%) was added, and 116.4 g (0.60 mol) of compound (S-1) and 1,208.0 g (0.40 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 1 (siloxane unit content 70.0% by mass). Polymer 1 had an Mw of 43,000. In addition, it was confirmed that the polymer 1 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-2] Synthesis of Polymer 2

After adding 79.5 g (0.30 mol) of compound (S-4) and 377.3 g (0.70 mol) of compound (S-3a) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device and reflux cooler, 2,000 g of toluene Was added and heated to 70°C. Thereafter, 1.0 g of toluene chloride solution (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Polymer 2 (siloxane unit content 20.1% by mass). Polymer 2 had an Mw of 83,000. In addition, it was confirmed that the polymer 2 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-3] Synthesis of Polymer 3

After adding 26.5 g (0.10 mol) of compound (S-4) and 485.1 g (0.90 mol) of compound (S-3a) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Then, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 135.8 g (0.70 mol) of compound (S-1) and 475.5 g (0.30 mol) of compound (S-2b) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Polymer 3 (siloxane unit content 42.3% by mass). Polymer 3 had an Mw of 8,000. In addition, it was confirmed that the polymer 3 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-4] Synthesis of Polymer 4

To a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, after adding 238.5 g (0.90 mol) of compound (S-4) and 53.9 g (0.10 mol) of compound (S-3a), 2,000 g of toluene Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.20 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Polymer 4 (siloxane unit content 57.4% by mass). The Mw of Polymer 4 was 143,000. In addition, it was confirmed that the polymer 4 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-5] Synthesis of Polymer 5

To a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 185.5 g (0.70 mol) of compound (S-4) and 254.5 g (0.30 mol) of compound (S-3b) were added, followed by 2,000 g of toluene. Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 77.6 g (0.40 mol) of compound (S-1) and 951.0 g (0.60 mol) of compound (S-2b) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Polymer 5 (siloxane unit content 65.2% by mass). Polymer 5 had an Mw of 23,000. In addition, it was confirmed that polymer 5 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-6] Synthesis of Polymer 6

After adding 132.5 g (0.50 mol) of compound (S-4) and 409.0 g (0.50 mol) of compound (S-3b) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2a) over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Polymer 6 (siloxane unit content 29.7 mass%). Polymer 6 had an Mw of 103,000. In addition, it was confirmed that the polymer 6 was a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Comparative Example 1-1] Synthesis of Comparative Polymer 1

After adding 212.0 g (0.80 mol) of compound (S-4) and 86.0 g (0.20 mol) of compound (S-6) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 184.3 g (0.95 mol) of compound (S-1) and 79.3 g (0.05 mol) of compound (S-2b) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 1 (siloxane unit content 14.1% by mass). The Mw of Comparative Polymer 1 was 8,000.

[Comparative Example 1-2] Synthesis of Comparative Polymer 2

After adding 212.0 g (0.80 mol) of compound (S-4) and 78.4 g (0.20 mol) of compound (S-5) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 38.8 g (0.20 mol) of compound (S-1) and 1,268.0 g (0.80 mol) of compound (S-2b) over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 2 (siloxane unit content: 79.4 mass%). The Mw of Comparative Polymer 2 was 85,000.

[Comparative Example 1-3] Synthesis of Comparative Polymer 3

After adding 431.2 g (0.80 mol) of compound (S-3a) and 86.0 g (0.20 mol) of compound (S-6) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Thereafter, 1.0 g of toluene chloride solution (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0.10 mol) of compound (S-2b) over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 3 (siloxane unit content: 18.6% by mass). The Mw of Comparative Polymer 3 was 28,000.

[Comparative Example 1-4] Synthesis of Comparative Polymer 4

After adding 654.4 g (0.80 mol) of compound (S-3b) and 78.4 g (0.20 mol) of compound (S-5) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2a) over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 4 (siloxane unit content 25.0 mass%). The Mw of Comparative Polymer 4 was 59,000.

[Comparative Example 1-5] Synthesis of Comparative Polymer 5

After adding 215.0 g (0.50 mol) of compound (S-6) and 196.0 g (0.50 mol) of compound (S-5) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added. Was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 135.8 g (0.70 mol) of compound (S-1) and 906.0 g (0.30 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 5 (siloxane unit content 62.4% by mass). The Mw of Comparative Polymer 5 was 93,000.

[Comparative Example 1-6] Synthesis of Comparative Polymer 6

After adding 430.0 g (1.00 mol) of compound (S-6) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.20 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain comparative polymer 6 (siloxane unit content: 50.8 mass%). The Mw of Comparative Polymer 6 was 67,000.

[Comparative Example 1-7] Synthesis of Comparative Polymer 7

To a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 392.0 g (1.00 mol) of compound (S-5) was added, and then 2,000 g of toluene was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.20 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 7 (siloxane unit content 52.5% by mass). The Mw of Comparative Polymer 7 was 100,000.

[Comparative Example 1-8] Synthesis of Comparative Polymer 8

After adding 265.0 g (1.00 mol) of compound (S-4) to a 10 L flask equipped with a stirrer, thermometer, nitrogen displacement device, and reflux cooler, 2,000 g of toluene was added and heated to 70°C. Thereafter, 1.0 g of a toluene chloride solution (platinum concentration 0.5 mass%) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.20 mol) of compound (S-2a) were added over 1 hour. Dropping was added (total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain Comparative Polymer 8 (59.0 mass% siloxane unit content). The Mw of Comparative Polymer 8 was 70,000.

(2) Light transmittance test

[Examples 2-1 to 2-6]

Polymers 1 to 6 were dissolved in cyclopentanone to a concentration of 50% by mass, respectively, to prepare a resin solution. Each resin solution was respectively coated on a glass wafer, heated at 60° C. for 30 minutes, and under nitrogen atmosphere at a temperature of 190° C. for 2 hours to prepare a resin film (thickness of 10 μm). About the obtained film, the light transmittance of wavelength 405 nm was measured using the spectrophotometer U-3900H (made by Hitachi High-Tech Science). Table 1 shows the results.

To the sample containing the coating on the glass wafer obtained by the above method, in a 50° C. oven, a laser having a wavelength of 405 nm and 1 W was irradiated for 100 hours and the optical transmittance after irradiating for 1,000 hours was measured. Table 2 shows the results.

From the above results, according to the present invention, a novel polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton, and a polyether skeleton in a main chain such as polymers 1 to 6 could be synthesized. The coating obtained from the siloxane polymer of the present invention can be used as a coating having high transparency and high light resistance.

[2] Preparation and evaluation of photosensitive resin composition

[Examples 3-1 to 3-10, Comparative Examples 2-1 to 2-19]

(1) Preparation of photosensitive resin composition

To the composition shown in Tables 3 to 5 below, (A) polymers 1 to 6 as components, comparative polymers 1 to 8, (B) photoacid generators as components B-1, B-2, (C) crosslinking agents as components C-1, C-2, C-3, (D) cyclopentanone (CP) as a solvent, and (E) component E-1, E-2 as an antioxidant, and then stirred and dissolved. Thereafter, fine filtration was performed with a 0.2 µm filter made of Teflon (registered trademark) to prepare a photosensitive resin composition.

In Tables 3 to 5, photo acid generators B-1 and B-2, crosslinking agents C-1, C-2 and C-3, and antioxidants E-1 and E-2 are as follows.

· Photoacid generator B-1:

Light acid generator B-2: CPI210S manufactured by Acid-Apro Corporation

・Crosslinking agent C-1, C-2, C-3:

Antioxidant E-1: CHIMASSORB 119FL (manufactured by BASF)

Antioxidant E-2: IRGANOX 3114 (manufactured by BASF)

(2) Pattern formation evaluation

Each photosensitive resin composition was coated with a film thickness of 10 μm using a spin coater on an 8-inch silicon wafer primed with hexamethyldisilazane. To remove the solvent from the composition, the wafer was placed on a hot plate and heated at 110° C. for 3 minutes to dry. The obtained photosensitive resin film was exposed through a mask using a contact aligner type exposure apparatus under an exposure condition of 365 nm to form a line and space pattern and a contact hole pattern. After light irradiation, PEB was performed at 120° C. for 3 minutes by a hot plate and then cooled, and the wafer was sprayed with propylene glycol monomethyl ether acetate (PGMEA) for 300 seconds to form a pattern.

The photosensitive resin film on the wafer on which the pattern was formed by the above method was post-cured while purging with nitrogen at 190°C for 2 hours using an oven. Thereafter, a cross section of a contact hole pattern of 50 µm, 30 µm, 20 µm, 10 µm, and 5 µm formed by a scanning electron microscope (SEM) was observed, and the smallest hole through which the hole penetrated to the bottom of the film. The pattern was defined as marginal resolution. In addition, from the obtained cross-sectional photograph, the verticality of the contact hole pattern of 50 µm was evaluated, the vertical pattern was ◎, the slightly reversed taper shape was ○, the reversed taper shape was △, and the defective opening was x. The results are shown in Tables 6 to 8.

(3) Light transmittance test 1

On the 8-inch glass wafer, each photosensitive resin composition was coated with a film thickness of 20 μm using a spin coater. In order to remove the solvent from the composition, the glass wafer was placed on a hot plate and heated at 110° C. for 3 minutes to dry. The entire surface of the composition applied to the glass wafer was not passed through a mask, and a mask aligner MA8 manufactured by Sousse Microtec was used, and after irradiating light with a high pressure mercury lamp (wavelength 360 nm) as a light source, PEB was performed and immersed in PGMEA. . The film remaining after this operation was further heated in an oven at 190°C for 2 hours to obtain a film. About this film, the transmittance of light with a wavelength of 405 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science). The results are shown in Tables 9 to 11.

(4) Light transmittance test 2

(3) Wavelength over time when a laser beam of 405 nm and 1 W was continuously shot in a 150° C. oven in a sample containing a film on a glass wafer obtained in the same manner as in the light transmittance test 1, and the initial value was 100%. The change in light transmittance after 2,000 hours at 405 nm was investigated. The results are shown in Tables 12 to 14.

(5) Evaluation of reliability (adhesion, crack resistance)

(3) Dicing saw (DAD685, manufactured by DISCO, spindle rotation speed is 40,000rpm, cutting speed is 20mm/sec) for a wafer with a photosensitive resin film obtained in the same manner as in the light transmittance test 1 is provided with a dicing blade. It cut|disconnected using it, and obtained the square test piece of 10 mm x 10 mm. The obtained test piece (each 10 pieces) was subjected to a heat cycle test (holding at -25°C for 10 minutes, holding at 125°C for 10 minutes was repeated 2,000 cycles), and the state of peeling of the resin film after the heat cycle test from the wafer, The presence or absence of crack was confirmed. It was good that no peeling or cracking occurred at all, and that peeling occurred even if one was peeled, and cracks were generated when cracking occurred even at one. The results are shown in Tables 15 to 17.

From the above results, the photosensitive resin composition of the present invention is capable of forming a fine pattern, exhibiting sufficient properties as a photosensitive material, and the coating has high light transmittance, and also has good light resistance and reliability (adhesion, crack resistance). , It was found to be useful as a material for an optical semiconductor device.

Claims (14)

A siloxane polymer containing a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in the main chain, and an epoxy group in the side chain. The siloxane polymer according to claim 1, wherein a transmittance of light having a wavelength of 405 nm of a film having a thickness of 10 µm including the polymer is 97% or more. The siloxane polymer according to claim 1 or 2, comprising repeating units represented by the following formulas (A1) to (A4).

[Wherein, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. m is an integer of 1 to 600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different from each other, and each R ⁴ may be the same or different from each other. a ¹ , a ² , a ³ and a ⁴ are 0<a ¹ <1, 0<a ² <1, 0<a ³ <1, 0<a ⁴ <1 and a ¹ +a ² +a ³ +a ^This is a number that satisfies ⁴ = 1. X ¹ is a divalent group represented by the following formula (X1). X ² is a divalent group represented by the following formula (X2).

(Wherein, R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group. n ¹ and n ² are each independently an integer of 0 to 7. R ¹³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and It may contain an ester bond or an ether bond between carbon atoms.)

(Wherein, R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group. p ¹ and p ² are each Independently, it is an integer from 1 to 6. q is an integer from 0 to 100.)] The siloxane polymer according to claim 3, wherein q is an integer from 5 to 20. The siloxane polymer according to claim 3, wherein m is an integer of 10 to 100. The siloxane polymer according to claim 3, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms. The siloxane polymer according to claim 1 or 2, having a weight average molecular weight of 3,000 to 500,000. (A) The photosensitive resin composition containing the siloxane polymer of (1) or (2) and (B) a photo acid generator. The photosensitive resin composition according to claim 8, wherein the content of the component (B) is 0.05 to 20 parts by mass based on 100 parts by mass of the component (A). The photosensitive resin composition according to claim 8, further comprising (C) a cationic polymerizable crosslinking agent. The photosensitive resin composition according to claim 8, further comprising (D) a solvent. The photosensitive resin composition according to claim 8, further comprising (E) an antioxidant. (i) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to claim 8,
(ii) the step of exposing the photosensitive resin film, and
(iii) Process of developing the exposed photosensitive resin film using a developer
Pattern formation method comprising a. The manufacturing method of the optical semiconductor element provided with the photosensitive resin film containing the pattern formation method of Claim 13.