TW202031742A - Siloxane polymer containing isocyanuric acid and polyether skeletons, photosensitive resin composition, pattern forming process, and fabrication of opto-semiconductor device - Google Patents

Abstract

A siloxane polymer comprising polysiloxane, silphenylene, isocyanuric acid, and polyether skeletons in a backbone and having an epoxy group in a side chain is provided. A photosensitive resin composition comprising the siloxane polymer and a photoacid generator is coated to form a film which can be patterned using radiation of widely varying wavelength. The patterned film has high transparency and light resistance.

Description

Silicone polymer containing isocyanuric acid skeleton and polyether skeleton, photosensitive resin composition, pattern forming method, and manufacturing method of optical semiconductor element

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

So far, in various optical devices represented by light-emitting diodes (LEDs), CMOS image sensors, etc., epoxy resins have been mainly used as seal protection materials. Among them, as those with high transparency and light resistance, most of them use epoxy-modified silicone resin, and there are also alicyclic epoxy resins introduced into the silphenylene skeleton. Type of base (Patent Document 1).

In terms of light resistance, even conventional devices are not a problem, but in recent years, optical devices such as LEDs are progressing towards higher output. Therefore, when using conventional seal protection materials, light resistance is insufficient and outgassing (outgas), discoloration, etc. In addition, in recent years, most of various optical devices require microfabrication. When performing such microfabrication, various resist materials such as epoxy resin materials are used. However, the aforementioned epoxy-modified silicone resin is not a material capable of performing fine processing of approximately 10 μm. As epoxy resins that can be applied to resist materials, there is a type in which two-terminal alicyclic epoxy modified silyl phenylene is introduced as a crosslinking agent (Patent Document 2), but it is more transparent In the case of the target, the heat resistance and light resistance cannot be said to be sufficient, and it is expected that a material that can withstand harsher conditions can be provided. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 8-32763 [Patent Document 2] JP 2012-001668 A

[The problem to be solved by the invention]

The present invention is an invention made in view of the foregoing circumstances. The object of the present invention is to provide a novel polymer that can impart a film with high transparency and high light resistance, and can form fine patterns with a wide range of wavelengths. A photosensitive resin composition capable of imparting a film with high transparency, high light resistance, and high heat resistance after pattern formation, a pattern forming method using the photosensitive resin composition, and a method for manufacturing an optical semiconductor element. [Means to solve the problem]

In order to achieve the foregoing objective, the inventors have repeatedly and in-depth research and found that: "The main chain contains a polysiloxane skeleton, a phenylene skeleton, an isocyanuric acid skeleton, and a polyether skeleton, and the side chain contains a ring A polymer composed of an oxy group can provide a film with high transparency and high light resistance, and a photosensitive resin composition containing the aforementioned polymer and a photoacid generator can be formed at a wide range of wavelengths At the same time as fine patterns, a film with high transparency, high light resistance, and high heat resistance can be provided after the pattern is formed", thus completing the present invention.

[式中，R¹ ~R⁴ 各自獨立為可包含雜原子的碳數1~20的一價烴基，m各自獨立為1~600的整數，當m為2以上的整數時，各R³ 可互為相同或相異，各R⁴ 可互為相同或相異，a¹ 、a² 、a³ 及a⁴ 為滿足下述式之數:0＜a¹ ＜1、0＜a² ＜1、0＜a³ ＜1、0＜a⁴ ＜1及a¹ +a² +a³ +a⁴ =1，X¹ 為下述式(X1)所表示的二價基，X² 為下述式(X2)所表示的二價基，

(式中，R¹¹ 及R¹² 各自獨立為氫原子或甲基，n¹ 及n² 各自獨立為0~7的整數，R¹³ 為碳數1~8的二價烴基，該碳原子間可包含酯鍵或醚鍵)

(式中，R²¹ 及R²² 各自獨立為氫原子或碳數1~8的一價烴基，R²³ 及R²⁴ 各自獨立為氫原子或甲基，p¹ 及p² 各自獨立為1~6的整數，q為0~100的整數)]。 4. 如3之矽氧烷聚合物，其中，q為5~20的整數。 5. 如3或4之矽氧烷聚合物，其中，m為10~100的整數。 6. 如3~5中任一項之矽氧烷聚合物，其中，R¹¹ 、R¹² 、R²¹ 及R²² 為氫原子。 7. 如1~6中任一項之矽氧烷聚合物，其中，重量平均分子量為3,000~500,000。 8. 一種感光性樹脂組成物，其包含(A)1~7中任一項之矽氧烷聚合物及(B)光酸產生劑。 9. 如8之感光性樹脂組成物，其中，相對於(A)成分100質量份，(B)成分的含有量為0.05~20質量份。 10. 如8或9之感光性樹脂組成物，其中，進一步包含(C)陽離子聚合性交聯劑。 11. 如8~10中任一項之感光性樹脂組成物，其中，進一步包含(D)溶劑。 12. 如8~11中任一項之感光性樹脂組成物，其中，進一步包含(E)抗氧化劑。 13. 一種圖型形成方法，其包含 (i)使用8~12中任一項之感光性樹脂組成物在基板上形成感光性樹脂皮膜之步驟、 (ii)將前述感光性樹脂皮膜進行曝光之步驟、及 (iii)將前述經曝光的感光性樹脂皮膜使用顯影液進行顯影之步驟。 14. 一種具備感光性樹脂皮膜的光半導體元件的製造方法，其包含13之圖型形成方法。 [發明的效果]Therefore, the present invention provides the following silicone polymer, photosensitive resin composition, pattern forming method, and manufacturing method of an optical semiconductor element. 1. A silicone polymer comprising a polysiloxane skeleton, a phenylene skeleton, an isocyanuric acid skeleton, and a polyether skeleton in the main chain, and an epoxy group in the side chain. 2. The silicone polymer described in 1, wherein a 10μm thick film containing the aforementioned polymer has a transmittance of 97% or more for light with a wavelength of 405nm. 3. The silicone polymer of 1 or 2, which contains repeating units represented by the following formulas (A1)~(A4),

[In the formula, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms that may contain heteroatoms, and m is each independently an integer of 1 to 600. When m is an integer of 2 or more, each R ³ may They are the same or different from each other, each R ⁴ can be the same or different from each other, a ¹ , a ² , a ³ and a ⁴ are numbers satisfying the following formula: 0＜a ¹ ＜1, 0＜a ² ＜1 , 0＜a ³ ＜1, 0＜a ⁴ ＜1 and a ¹ + a ² + a ³ + a ⁴ =1, X ¹ is a divalent group represented by the following formula (X1), and X ² is the following The divalent group represented by 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 from 0 to 7, and R ¹³ is a divalent hydrocarbon group with 1 to 8 carbon atoms. Contains ester bond or ether bond)

(In the formula, R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 8 carbon atoms, R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group, and p ¹ and p ² are each independently 1 to 6. Is an integer of 0~100)]. 4. Silicone polymer such as 3, where q is an integer from 5 to 20. 5. Such as 3 or 4 silicone polymer, where m is an integer from 10 to 100. 6. The silicone polymer of any one of 3 to 5, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms. 7. The silicone polymer of any one of 1 to 6, wherein the weight average molecular weight is 3,000 to 500,000. 8. A photosensitive resin composition comprising (A) the silicone polymer of any one of 1 to 7 and (B) a photoacid generator. 9. The photosensitive resin composition according to 8, wherein the content of the component (B) is 0.05 to 20 parts by mass relative to 100 parts by mass of the component (A). 10. The photosensitive resin composition according to 8 or 9, which further contains (C) a cationically polymerizable crosslinking agent. 11. The photosensitive resin composition according to any one of 8 to 10, which further contains (D) a solvent. 12. The photosensitive resin composition according to any one of 8 to 11, which further contains (E) antioxidant. 13. A pattern forming method comprising (i) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of any one of 8 to 12, and (ii) exposing the aforementioned photosensitive resin film Step and (iii) the step of developing the above-mentioned exposed photosensitive resin film using a developing solution. 14. A method of manufacturing an optical semiconductor element provided with a photosensitive resin film, including the pattern forming method of 13. [Effects of the invention]

The silicone polymer of the present invention can be easily synthesized and can provide a film with high transparency and high light resistance. In addition, by using a photosensitive resin composition containing the aforementioned polymer and a photoacid generator, a film can be easily formed without being hindered by oxygen, and the film can be exposed to light of a wide range of wavelengths, so it can be formed Subtle graphics. Furthermore, the film obtained from the photosensitive resin composition of the present invention is also excellent in transparency, light resistance, and heat resistance, and can be suitably used for the protection and sealing of optical semiconductor elements and the like.

[Best form to implement invention] [Silicone Polymer]

The silicone polymer of the present invention includes a polysiloxane skeleton, a phenylene phenylene 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, repeating units represented by the following formulas (A1) to (A4) (hereinafter also referred to as "repeating units A1 to A4" respectively) are preferred.

In the formulas (A2) and (A4), R ¹ to R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms that may include a hetero atom. m is independently an integer from 1 to 600. 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. In the repeating units A2 and A4, if there are 2 or more siloxane units, the siloxane units may all be the same, or may include two or more different siloxane units. If two or more different siloxane units are included (that is, when m is an integer of 2 or more), the siloxane units may be randomly bonded, alternatively bonded, or may be It is a block containing a plurality of silicone units of the same kind.

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

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

In addition, the monovalent aliphatic hydrocarbon group may include heteroatoms. Specifically, part or all of the hydrogen atoms of the monovalent aliphatic hydrocarbon group may be replaced by halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Substitution, or the inter-carbon atom system may insert a carbonyl group, ether bond, thioether bond, etc. Examples of such monovalent aliphatic hydrocarbon groups containing heteroatoms include 2-oxocyclohexyl (2-oxocyclohexyl) and the like.

Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethyl Phenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, naphthyl, biphenyl, tertphenyl, etc. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

In addition, the aforementioned monovalent aromatic hydrocarbon group may contain heteroatoms. Specifically, part or all of the hydrogen atoms of the aforementioned monovalent aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms. Alkylthio, aryloxy with 6 to 20 carbons, arylthio with 6 to 20 carbons, etc. are substituted.

Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, n-pentoxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy , N-nonyloxy, n-decyloxy, norbornyloxy, adamantyloxy, etc.

Examples of the aforementioned alkylthio group having 1 to 10 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropylthio, n-butylthio, and isobutylthio. , Sec-butylthio, tert-butylthio, cyclobutylthio, n-pentylthio, cyclopentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, n-octylthio Group, n-nonylthio, n-decylthio, norbornylthio, adamantylthio, etc.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, and 2-ethylphenoxy. , 3-ethylphenoxy, 4-ethylphenoxy, 4-tert-butylphenoxy, 4-butylphenoxy, dimethylphenoxy, naphthyloxy, biphenyloxy Group, terphenyloxy, etc.

Examples of the arylthio group having 6 to 20 carbon atoms include phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-ethylphenylthio , 3-ethylphenylthio, 4-ethylphenylthio, 4-tert-butylphenylthio, 4-butylphenylthio, dimethylphenylthio, naphthylthio, biphenylthio Group, terphenylthio group, etc.

For example, as aryl groups substituted by these groups, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3 -Ethoxyphenyl, 4-ethoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, biphenyloxyphenyl, biphenylthiophenyl Wait.

The carbon number of the aforementioned monovalent aliphatic hydrocarbon group is preferably 1-10, and more preferably 1-8. Furthermore, the carbon number of the aforementioned monovalent aromatic hydrocarbon group is preferably 1-14, and more preferably 1-10.

Among these, R ¹ to R ^{4 are} preferably methyl, ethyl, n-propyl or phenyl, and more preferably methyl or phenyl.

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

In formulas (A1) to (A4), a ¹ , a ² , a ³ and a ⁴ are numbers satisfying the following formula: 0<a ¹ ＜1, 0＜a ² ＜1, 0＜a ³ ＜1 0<a ⁴ <1 and a ¹ +a ² +a ³ +a ⁴ =1. Preferably, it is a number that satisfies the following formulas: 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; it is more preferable to satisfy the following formula: 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≦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 the 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 0-7.

In the formula (X1), R ¹³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and the inter-carbon system may include an ester bond or an ether bond. The aforementioned divalent hydrocarbon group may be arbitrarily linear, branched, or cyclic, and specific examples include methylene group, ethane-1,1-diyl, and ethane-1,2 -Diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-di Alkyl and other groups. In addition, an ester bond or ether bond may be inserted between the carbon atoms of the aforementioned divalent hydrocarbon group. Among them, R ^{13 is} preferably a methylene group or an ethylene group, and more preferably a methylene group.

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 C 1-8 monovalent hydrocarbon group. 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, preferably an integer of 1 to 4, and more preferably 1 or 2. q is an integer of 0-100, preferably an integer of 1-50, and more preferably an integer of 5-20.

The aforementioned monovalent hydrocarbon group with 1 to 8 carbons may be arbitrarily linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 8 carbons, alkenyl groups with 2 to 8 carbons, etc. Monovalent aromatic hydrocarbon groups such as monovalent aliphatic hydrocarbon groups, aryl groups having 6 to 8 carbon atoms, and aralkyl groups having 7 or 8 carbon atoms.

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

Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethyl Phenyl, dimethylphenyl, etc. Examples of the aforementioned aralkyl group include benzyl and phenethyl.

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 formula (X2), the alkylene oxide unit represented by the suffix q may be randomly bonded, alternatively bonded, or may include plural alkylene oxides of the same species. Block of oxygen units.

The weight average molecular weight (Mw) of the silicone polymer of the present invention is preferably 3,000 to 500,000, and more preferably 5,000 to 200,000. As long as Mw is in the aforementioned range, the polymer can be obtained as a solid, and film-forming properties can also be ensured. Furthermore, in the present invention, Mw is a measured value obtained in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a dissolving agent.

In the silicone polymer of the present invention, the repeating units A1 to A4 may be randomly bonded, or may be alternately bonded, or may be a block including a plurality of units. In addition, in the silicone polymer of the present invention, the content of the silicone unit is preferably 10 to 90% by mass.

[Manufacturing method of silicone polymer] The compound represented by the following formula (1) (hereinafter also referred to as "compound (1)") and the compound represented by the following formula (2) (hereinafter also referred to as " Compound (2)”), the compound represented by the following formula (3) (hereinafter also referred to as “compound (3)”) and the compound represented by the following formula (4) (hereinafter also referred to as “compound (4) ") Perform addition polymerization to produce the silicone polymer of the present invention.

(式中，R¹ ~R⁴ 、R¹¹ ~R¹³ 、R²¹ ~R²⁴ 、m、n¹ 、n² 、p¹ 、p² 及q係與前述為相同)。

(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 described above).

As the aforementioned metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metals can be used; 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 (here, x is better It is an integer of 0-6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid, and chloroplatinate; alcohol-modified chloroplatinic acid (for example, described in the specification of US Patent No. 3,220,972); Complexes of chloroplatinic acid and olefins (for example, those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); platinum group metals such as platinum black or palladium are supported on Carriers of alumina, silicon dioxide, carbon, etc.; rhodium-olefin complexes; chloroginseng (triphenylphosphine) rhodium (so-called Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate Complexes with vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes), etc.

The amount of the catalyst used is the amount of the catalyst, and generally speaking, in the total mass of the compounds (1) to (4), the platinum group metal is preferably 0.001 to 0.1% by mass.

In the aforementioned polymerization reaction, a solvent can be used as needed. As the solvent, hydrocarbon solvents such as toluene and xylene are preferred. As the aforementioned polymerization conditions, the polymerization temperature is, for example, 40 to 150°C, particularly preferably 60 to 120°C, from the viewpoint of not deactivating the catalyst and completing the polymerization in a short time. The polymerization time will vary depending on the type and amount of the raw material compound, but in order to prevent moisture from entering the polymerization system, it is better to complete the reaction in about 0.5 to 100 hours, especially 0.5 to 30 hours. After finishing the polymerization reaction in this way, if a solvent is used, it is distilled off to obtain the aforementioned polymer.

The reaction method is not particularly limited, as long as the compound (3) and the compound (4) are first mixed and heated, then the metal catalyst is added to the aforementioned mixed solution, and then the compound (1) and the compound (1) and are dropped in 0.1 to 5 hours. Compound (2) is sufficient.

Each raw material compound may be formulated in such a way as to be: in molar ratio, compound (1) and compound (2) relative to the total of alkenyl groups possessed by compound (3) and compound (4) The hydrosilyl group is preferably 0.67 to 1.67, and more preferably 0.83 to 1.25. Monoallyl compounds like o-allylphenol, or monohydrosiloxanes or monohydrosiloxanes like triethylhydrosiloxane can be used as molecular weight modifiers to control the silicone polymer of the present invention Mw.

[Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) the aforementioned silicone polymer and (B) a photoacid generator. (A) The silicone polymer of the component may be used alone or in combination of two or more kinds.

[(B) Photoacid generator] The photoacid generator of component (B) is not particularly limited, as long as it can be decomposed by light irradiation to generate acid, and it is preferably a photoacid generator that can generate acid by irradiating light with a wavelength of 190 to 500 nm . (B) The photoacid generator is used as a curing catalyst. Examples of the aforementioned photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfonate derivatives, disulfonate derivatives, and nitrobenzyl sulfonate derivatives. , Sulfonate derivatives, iminium-based-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc.

Examples of the onium salt include a sulfonium salt represented by the following formula (B1) or an iodonium salt represented by the following formula (B2).

In formulas (B1) and (B2), R ¹⁰¹ to R ¹⁰⁵ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted carbon number 6 to 12 aryl group, or an optionally substituted group The C7-12 aralkyl group. A ^{-is a} non-nucleophilic relative ion.

The aforementioned alkyl group may be arbitrarily linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec -Butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. As said aryl group, a phenyl group, a naphthyl group, a biphenyl group, etc. are mentioned. As said aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

Examples of the aforementioned substituent include oxo group, linear, branched or cyclic alkoxy group having 1 to 12 carbons, and linear, branched or cyclic carbon number of 1 to 1 12 alkyl groups, aryl groups having 6 to 24 carbons, aralkyl groups having 7 to 25 carbons, aryloxy groups having 6 to 24 carbons, arylthio groups having 6 to 24 carbons, and the like.

R ¹⁰¹ to R ^{105 are} preferably alkyl groups that may have substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; benzene Group, naphthyl, biphenyl, o-, m- or p-methoxyphenyl, ethoxyphenyl, m- or p-tert-butoxyphenyl, 2-, 3- or 4- Methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, biphenylsulfanylbenzene Substitutable aryl groups such as a group; aralkyl groups such as a benzyl group and a phenethyl group which may have a substituent. Among these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are also preferable.

Examples of the non-nucleophilic relative ion include halide ions such as chloride ion and bromide ion; triflate ion, 1,1,1-trifluoroethanesulfonate ion, nonafluoromethane Fluoroalkane sulfonate ion such as butanesulfonate ion; toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate Arylsulfonate ion such as acid salt ion; alkanesulfonate ion such as methanesulfonate ion and butanesulfonate ion; fluoroalkanesulfonimide ion such as trifluoromethanesulfonamide ion; Fluoroalkane sulfonyl methide ions such as ginseng (trifluoromethanesulfonyl) methide ion; borate ions such as phenyl borate ion and tetrafluorophenyl 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 carbons or a halogenated alkyl group, an optionally substituted aryl group having 6 to 12 carbons, or an aryl group having 7 to 12 carbons. alkyl.

As the aforementioned alkyl group, the same ones as exemplified in the description of R ¹⁰¹ to R ¹⁰⁵ can be mentioned. Examples of the halogenated alkyl group include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, and the like.

Examples of the aforementioned aryl group which may have a substituent include phenyl; 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert -Alkoxyphenyl such as butoxyphenyl; 2-, 3- or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethyl Alkylphenyl groups such as phenyl group; halogenated aryl groups such as fluorophenyl group, chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group, etc. 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 the formula (B4), R ¹²¹ to R ¹²⁴ are each independently an alkyl group having 1 to 12 carbons or a halogenated alkyl group, an optionally substituted aryl group having 6 to 12 carbons, or an aryl group having 7 to 12 carbons. alkyl. In addition, R ¹²³ and R ¹²⁴ can be bonded to each other and form a ring with the bonded carbon atoms. If a ring is formed, the group formed by the bonding of R ¹²³ and R ¹²⁴ is a group with 1 to 12 carbon atoms. Linear or branched alkylene.

Examples of the aforementioned alkyl group, halogenated alkyl group, optionally substituted aryl group, and aralkyl group include the same ones as those exemplified as R ¹¹¹ and R ¹¹² . Examples of the linear or branched alkylene group include methylene, ethylene, propylene, butylene, and hexylene.

Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, and diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl) phenyl iodonium p-toluenesulfonate, triphenyl sulfonate trifluoromethanesulfonate, (p-tert-butoxyphenyl) ) Diphenyl sulfonate trifluoromethane sulfonate, bis (p-tert-butoxyphenyl) phenyl sulfonate trifluoromethane sulfonate, ginseng (p-tert-butoxy phenyl) sulfonate trifluoromethane Sulfonate, triphenyl sulfonate p-toluenesulfonate, (p-tert-butoxyphenyl) diphenyl sulfonate p-toluenesulfonate, bis(p-tert-butoxyphenyl) benzene P-toluenesulfonate, ginseng (p-tert-butoxyphenyl) p-toluenesulfonate, triphenylsulfonate nonafluorobutanesulfonate, triphenylsulfonate, triphenylsulfonate Methyl sulfonate trifluoromethanesulfonate, trimethyl sulfonium p-toluenesulfonate, cyclohexyl methyl (2-oxocyclohexyl) sulfonate, cyclohexyl methyl (2-oxo Cyclohexyl) sulfonium p-toluenesulfonate, dimethyl phenyl sulfonium trifluoromethanesulfonate, dimethyl phenyl sulfonium p-toluenesulfonate, dicyclohexyl phenylsulfonium trifluoromethanesulfonate, Dicyclohexylphenyl sulfonium p-toluenesulfonate, bis(4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyl (4-thiophenoxyphenyl) hexafluoroantimonic acid Salt, [4-(4-biphenylsulfanyl)phenyl]-4-biphenylphenyl ginseng (trifluoromethanesulfonyl) methide, triphenyl sulfonium (fluorophenyl) boric acid Salt, ginseng [4-(4-acetylphenyl) phenylsulfanyl] sulfonate (fluorophenyl) borate, triphenyl sulfonate (pentafluorophenyl) borate, ginseng [4-(4- Acetyl phenyl) phenylthio] sulfa (pentafluorophenyl) borate and the like.

As the aforementioned diazomethane derivatives, specifically, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, Bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane Methane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl) Diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis( tert-pentylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentyl) Sulfonyl) diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl) diazomethane and the like.

Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime and 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 ethylenedioxime, bis-o-(n-butanesulfonyl)-α-dimethylethyl Dioxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o -(n-butanesulfonyl)-2,3-pentanedione ethylenedioxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione ethylenedioxime, Bis-o-(methylsulfonyl)-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-(cyclohexylsulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethyl Glyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethyl Glyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

Specific examples of the aforementioned β-ketosulfonyl derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl) Propane etc.

Specific examples of the disulfide derivatives include diphenyl disulfide, dicyclohexyl disulfide, and the like.

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

Specific examples of the sulfonate derivatives include 1,2,3-gins(methylsulfonyloxy)benzene, 1,2,3-gins(trifluoromethanesulfonyloxy)benzene, 1, 2,3-ginseng (p-toluenesulfonyloxy)benzene and the like.

As the aforementioned imidimine-based-sulfonate derivative, specifically, phthalimide-based-trifluoromethanesulfonate, phthalimide-based-toluenesulfonic acid Salt, 5-norbornene-2,3-dicarboxyimid-yl-trifluoromethanesulfonate, 5-norbornene-2,3-dicarboxyimid-yl-toluenesulfonate, 5-Norbornene-2,3-dicarboxyamido-n-butanesulfonate, n-trifluoromethanesulfonyloxynaphthylimide, etc.

Specific examples of the oxime sulfonate derivative include α-(phenyloxyimino)-4-methylphenylacetonitrile.

As the aforementioned iminosulfonate derivative, specifically (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) Phenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methyl Phenyl)-acetonitrile and the like.

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

As the photoacid generator of the component (B), the aforementioned onium salt is particularly preferred, and the aforementioned sulphur salt is more preferred.

The content of the (B) component is preferably 0.05 to 20 parts by mass, and more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the (A) component. As long as the content of the component (B) is in the aforementioned range, sufficient photocurability can be easily obtained, and furthermore, it is possible to effectively prevent the deterioration of the curability during thick film due to the light absorption of the photoacid generator itself. Furthermore, in order to obtain the characteristic transparency and light resistance of the present invention, the blending amount of the photoacid generator of the component (B) having light absorption properties should be as small as possible within a range that does not hinder the photocurability. (B) The photoacid generator of a component may be used individually by 1 type, and may be used in combination of 2 or more types.

[(C) Cationic polymerizable crosslinking agent] The photosensitive resin composition of the present invention may further include a cationically polymerizable crosslinking agent as the (C) component. The aforementioned cationic polymerizable crosslinking agent is a component that can cause a cationic polymerization reaction with the epoxy group of the component (A) to facilitate the formation of a pattern, and it is also a component that can further increase the strength of the resin film after light curing .

As the aforementioned crosslinking agent, a compound having a molecular weight of 100 to 15,000 is preferable, and a compound having a molecular weight of 200 to 1,000 is more preferable. As long as the molecular weight is 100 or more, sufficient photocurability can be obtained, and as long as it is 15,000 or less, the heat resistance after photocuring of the composition is not likely to deteriorate, so it is preferred. Furthermore, the aforementioned compound may also be a resin (polymer), and in this case, the molecular weight is the weight average molecular weight (Mw).

As the aforementioned cationic polymerizable crosslinking agent, a compound having a functional group selected from an epoxy group, an oxetane group, and a vinyl ether group is preferred. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

With respect to 100 parts by mass of (A) component, the content of (C) component is 0-100 parts by mass, if contained, it is preferably 0.5-100 parts by mass, more preferably 0.5-60 parts by mass, and more preferably 1-50 parts by mass. If the content of the component (C) is 0.5 parts by mass or more, sufficient curability can be obtained during light irradiation, and as long as it is 100 parts by mass or less, the ratio of the component (A) in the photosensitive resin composition will not decrease. The hardened product can fully exhibit the effects of the present invention. (C) A component system may be used individually by 1 type, and may be used in combination of 2 or more types.

[(D) Solvent] In order to improve the coatability of the photosensitive resin composition of this invention, you may contain a solvent as (D) component. The (D) solvent is not particularly limited as long as it can dissolve the aforementioned (A) to (C) components, the (E) component described below, or other various additives.

As the solvent (D), organic solvents are preferred. Specific examples include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; 3-methoxybutanol , 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and other alcohols; propylene glycol monomethyl ether, ethylene glycol mono Methyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate , Propylene glycol-mono-tert-butyl ether acetate, γ-butyrolactone and other esters. These solvents may be used individually by 1 type, and may mix and use 2 or more types.

As the (D) solvent, especially ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixtures thereof, which are excellent in the solubility of the photoacid generator The solvent is preferred.

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

[(E) Antioxidant] The photosensitive resin composition of the present invention may contain an antioxidant as an additive. By including antioxidants, heat resistance can be improved. As said antioxidant, hindered phenol type compound, hindered amine type compound, etc. are mentioned.

The hindered phenol-based compound is not particularly limited, but it is preferably those exemplified below. For example, 1,3,5-trimethyl-2,4,6-ginseng (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 (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'- Methyl bis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonic acid-diethyl Esters (trade name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2'-methylene bis(4 -Ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylene 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)( Trade name: Seenox 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-reference- (2-Methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: AdekaStab AO-30), tetramethylene-(3,5-di-tert-butyl-4 -Hydroxyhydrocinnamate)] methane (trade name: AdekaStab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (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-hexanediol-bis(3-(3 ,5-Di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-diethylene bis[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methyl Phenyl) propionyloxy] 1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), Ref-(3 ,5-Di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate) Ester) calcium/polyethylene wax mixture (50:50) (trade name: IRGANOX 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (commodity 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-butyl dibenzo[d,f][1,3,2]dioxaphosphorus Dioxaphosphepin (trade name: Sumilizer GP) and the like.

The aforementioned hindered amine compound is not particularly limited, but is preferably one exemplified below. Examples include p,p'-dioctyl diphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl -1,2-dihydroquinoline) (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'-bis-β-naphthyl-p-phenylenediamine (trade name :Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine ( Trade name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac CD), p,p-toluenesulfonylamino diphenylamine ( Trade name: Nocrac TD), N-phenyl-N'-(3-methacryloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-( 1-Methylheptyl)-N'-phenyl-p-phenylene diamine (trade name: Ozonon 35), N,N'-bis-sec-butyl-p-phenylene diamine (commodity Name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl succinate-1-(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-pyridinyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-pyridinyl)imino]] (trade name: CHIMASSORB 944), N, N '-Bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-pyridinyl)amine Yl)-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-pyridinyl ) Sebacate (trade name: TINUVIN 123), bis(2,2,6,6-tetramethyl-4-pyridinyl) sebacate (trade name: TINUVIN 770), 2-(3, 5-Di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-pyridinyl) (commodity Name: TINUVIN 144), double (1,2,2,6,6-pentamethyl-4 -Pyridinyl) sebacate (trade name: TINUVIN 765), Si (1,2,2,6,6-pentamethyl-4-pyridinyl)1,2,3,4-butane tetra Carboxylic acid ester (trade name: LA-57), Si (2,2,6,6-tetramethyl-4-pyridinyl) 1,2,3,4-butane tetracarboxylic acid ester (trade name: LA-52), 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-pyridinol and 1-tridecyl alcohol mixed ester (commodity Name: LA-62), 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-pyridinol and 1-tridecanol mixed ester (commodity Name: LA-67), 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-pyridinol and 3,9-bis(2-hydroxyl -1,1-Dimethylethyl)-2,4,8,10-Tetraoxaspiro[5.5]undecane mixed ester compound (trade name: LA-63P), 1,2,3,4 -Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-pyridinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4, Mixed esters of 8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), (2,2,6,6-tetramethylene-4-pyridinyl)-2- Propylene carboxylate (trade name: AdekaStab LA-82), (1,2,2,6,6-pentamethyl-4-pyridinyl)-2-propene carboxylate (trade name: AdekaStab LA-87 )Wait.

The content of the component (E) is not particularly limited as long as the effect of the present invention is not impaired. If contained, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention. (E) The antioxidant of the component may be used alone or in combination of two or more kinds.

[Other additives] In addition to the aforementioned components, the photosensitive resin composition of the present invention may contain other additives. Examples of additives include surfactants that are commonly used to improve coatability.

The surfactant is preferably a nonionic surfactant, for example, a fluorine-based surfactant, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl Amine oxides, fluorine-containing organosiloxane compounds, etc. Such commercially available ones include, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical (stock)), Unidye (registered trademark) ) DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries (stock)), Megaface (registered trademark) F-8151 (manufactured by DIC (stock)), X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.) )Wait. Among them, Fluorad FC-430 and X-70-093 are preferred. The content of the aforementioned surfactant is not particularly limited as long as the effect of the present invention is not impaired. If contained, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

In addition, a silane coupling agent can also be used as an additive. By including the silane coupling agent, the adhesion of the photosensitive resin composition to the adherend can be further improved. As a silane coupling agent, an epoxy silane coupling agent, an aromatic-containing amino silane coupling agent, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types. The content of the silane coupling agent is not particularly limited as long as it does not impair the effects of the present invention. If it is contained, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

The preparation method of the photosensitive resin composition of the present invention is not particularly limited. For example, a method of stirring and mixing the aforementioned components, and then filtering with a filter or the like for removing solid content as required can be mentioned.

[Pattern Formation Method] The pattern forming method of the present invention uses the aforementioned photosensitive resin composition and includes the following steps: (i) The step of forming a photosensitive resin film on a substrate using the aforementioned photosensitive resin composition, (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the above-mentioned exposed photosensitive resin film using a developing solution. With this method, fine patterns can be obtained.

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

The photosensitive resin film can be formed by a well-known method. For example, it can be formed by applying the aforementioned photosensitive resin composition to a substrate by a method such as a dipping method, a spin coating method, and a roll coating method. The coating amount can be appropriately selected according to the purpose, but it is preferable that the film thickness becomes 0.1-100 μm.

Here, in order to efficiently carry out the photohardening reaction, the solvent and the like can be pre-evaporated by preheating as needed. The preheating can be performed, for example, at 40 to 160°C for about 1 minute to 1 hour.

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

Exposure can also be performed through a photomask. The aforementioned photomask may be, for example, a photomask having a desired pattern cut through. Furthermore, the material of the photomask is preferably capable of shielding light with the aforementioned wavelength of 240 to 500 nm. For example, chromium can be suitably used, but it is not limited to this.

Furthermore, in order to improve the development sensitivity, heat treatment (PEB) may be performed after exposure. PEB can be carried out at 40 to 160°C for 5 to 30 minutes, for example.

Step (iii) is a step of developing the photosensitive resin film using a developing solution after exposure or PEB. The developer is preferably an organic solvent-based developer used as a solvent, for example, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. By using the aforementioned organic solvent-based developer for development, it is possible to obtain a negative pattern in which the non-exposed portion is dissolved and removed. The development can be performed by a usual method, for example, immersing a patterned substrate in the aforementioned developer. After that, washing, rinsing, drying, etc. are performed as needed, and a film having a desired pattern can be obtained.

However, the pattern formation method is the same as described above, but if there is no need to form a pattern, for example, when only a uniform film is to be formed, in step (ii) of the aforementioned pattern formation method, as long as not What is necessary is just to expose with light of an appropriate wavelength through the said mask, and to form a film.

Furthermore, if necessary, the following treatment (post-curing) can also be used to increase the crosslinking density and remove the remaining volatile components: (iv) The patterned film is further used in an oven or a heating plate to 120 Heat at ~300℃ for 10 minutes to 10 hours.

[Optical Semiconductor Device] The photosensitive resin composition is used and the fine pattern is formed by the aforementioned method, whereby an optical semiconductor device can be manufactured. In addition, the film obtained from the aforementioned photosensitive resin composition is excellent in transparency, light resistance and heat resistance, and the optical semiconductor element provided with the film is suitable for use in light-emitting elements such as light-emitting diodes, photodiodes, and optical sensors , Optical devices such as light-receiving elements such as CMOS image sensors, and optical transmission devices such as optical waveguides. For light with a wavelength of 405 nm, the transmittance of the aforementioned film is preferably 92% or more, more preferably 96% or more, and particularly preferably 98% or more. [Example]

The following shows examples and comparative examples to further illustrate the present invention, but the present invention is not limited to the following examples. Furthermore, in the following examples, by using TSKGEL Super HZM-H (manufactured by Tosoh Co., Ltd.) as the GPC column, under the analysis conditions of flow rate 0.6 mL/min, eluent THF, and column temperature of 40°C, Mw was measured by GPC using monodisperse polystyrene as a standard.

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

[1] Synthesis and evaluation of polymer (1) Synthesis of polymer [Example 1-1] Synthesis of polymer 1 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux cooler, the compound (S -4) After 132.5 g (0.50 mol) and 269.5 g (0.50 mol) of compound (S-3a), 2,000 g of toluene was added, and the mixture was heated to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dropping was completed, the mixture was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 1 (silicone unit content rate 70.0% by mass). The Mw of polymer 1 was 43,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 1 was a polymer containing repeating units A1 to A4.

[Example 1-2] Synthesis of polymer 2 79.5 g (0.30 mol) of compound (S-4) and compound (S-3a) were added to a 10-L flask equipped with a stirrer, thermometer, nitrogen substitution device, and reflux cooler After 377.3 g (0.70 mol), 2,000 g of toluene was added and heated to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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) were dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 2 (silicone unit content rate 20.1% by mass). The Mw of polymer 2 was 83,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 2 was a polymer containing repeating units A1 to A4.

[Example 1-3] Synthesis of polymer 3 26.5 g (0.10 mol) of compound (S-4) and compound (S-3a) were added to a 10 L flask equipped with a stirrer, thermometer, nitrogen substitution device, and reflux cooler After 485.1 g (0.90 mol), 2,000 g of toluene was added and heated to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 3 (silicone unit content rate 42.3% by mass). The Mw of polymer 3 was 8,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 3 is a polymer containing repeating units A1 to A4.

[Example 1-4] Synthesis of polymer 4 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux cooler, 238.5 g (0.90 mol) of compound (S-4) and compound (S-3a) were added After 53.9 g (0.10 mol), 2,000 g of toluene was added and heated to 70°C. After that, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, the mixture was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 4 (silicone unit content rate 57.4% by mass). The Mw of polymer 4 was 143,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 4 is a polymer containing repeating units A1 to A4.

[Example 1-5] Synthesis of polymer 5 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux cooler, 185.5 g (0.70 mol) of compound (S-4) and compound (S-3b) were added After 254.5 g (0.30 mol), 2,000 g of toluene was added and heated to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 5 (silicone unit content rate 65.2% by mass). The Mw of polymer 5 was 23,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 5 was a polymer containing repeating units A1 to A4.

[Example 1-6] Synthesis of polymer 6 132.5 g (0.50 mol) of compound (S-4) and compound (S-3b) were added to a 10 L flask equipped with a stirrer, thermometer, nitrogen substitution device, and reflux cooler After 409.0 g (0.50 mol), 2,000 g of toluene was added, and it heated to 70 degreeC. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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) were dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain polymer 6 (silicone unit content rate of 29.7% by mass). The Mw of polymer 6 was 103,000. It was confirmed by ¹ H-NMR (manufactured by Bruker) that polymer 6 was a polymer containing repeating units A1 to A4.

[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 substitution device, and reflux cooler, 2,000 toluene was added g, heat to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, the mixture was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 1 (silicone unit content rate 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 substitution device and reflux cooler, 2,000 toluene was added g, heat to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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) were dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100° C. and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 2 (silicone unit content rate of 79.4% by mass). The Mw of Comparative Polymer 2 was 85,000.

[Comparative Example 1-3] Synthesis of Comparative Polymer 3 Put 431.2g (0.80 mol) of compound (S-3a) and 86.0g (0.20 mol) of compound (S-6) into a 10L flask equipped with a stirrer, thermometer, nitrogen substitution device, and reflux cooler, and then add 2,000 toluene g, heat to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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) were dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 3 (silicone unit content rate of 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 substitution device and reflux cooler, 2,000 toluene was added g, heat to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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) were dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 4 (silicone unit content rate of 25.0% by 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 substitution device and reflux cooler, 2,000 toluene was added g, heat to 70°C. After that, 1.0 g of chloroplatinic acid toluene solution (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 5 (silicone unit content rate 62.4% by mass). The Mw of Comparative Polymer 5 was 93,000.

[Comparative Example 1-6] Synthesis of Comparative Polymer 6 After putting 430.0 g (1.00 mol) of compound (S-6) in a 10-L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux cooler, 2,000 g of toluene was added, and the mixture was heated to 70°C. After that, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, the mixture was heated to 100° C. and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 6 (silicone unit content rate of 50.8% by mass). The Mw of Comparative Polymer 6 was 67,000.

[Comparative Example 1-7] Synthesis of Comparative Polymer 7 After adding 392.0 g (1.00 mol) of compound (S-5) to a 10-L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux cooler, 2,000 g of toluene was added, and the mixture was heated to 70°C. After that, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off under reduced pressure from the reaction solution to obtain a comparative polymer 7 (silicone unit content rate of 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, a thermometer, a nitrogen substitution device, and a reflux cooler, 2,000 g of toluene was added, and the mixture was heated to 70°C. After that, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by 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 dropped over 1 hour. (Total of hydrosilyl groups/total of alkenyl groups = 1/1 (molar ratio)). After the dripping was completed, it was heated to 100°C and matured for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a comparative polymer 8 (silicone unit content rate of 59.0% by mass). The Mw of Comparative Polymer 8 was 70,000.

(2) Light transmittance test [Examples 2-1~2-6] Each of polymers 1 to 6 was dissolved in cyclopentanone so that the concentration became 50% by mass to prepare a resin solution. Each resin solution was applied on a glass wafer, heated at 60°C for 30 minutes, and further heated at a temperature of 190°C in a nitrogen atmosphere for 2 hours to produce a resin film (thickness 10 μm). For the obtained film, a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science) was used to measure the light transmittance at a wavelength of 405 nm. The results are shown in Table 1.

A sample composed of a film on a glass wafer obtained by the aforementioned method was irradiated with a laser with a wavelength of 405nm and 1W for 100 hours and 1000 hours in an oven at 50°C to measure the light transmittance after 100 hours of irradiation, and Light transmittance after 1000 hours of irradiation. The results are shown in Table 2.

From the above results, it can be seen that by the present invention, a novel polymer containing a polysiloxane skeleton, a silylene skeleton, an isocyanuric acid skeleton, and a polyether skeleton in the main chain can be synthesized like polymers 1 to 6 Of polymers. The film obtained from the silicone polymer of the present invention can be used as a film with 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 The polymer 1 to 6 as the component (A), the comparative polymer 1 to 8, and the photoacid generator B-1 as the component (B) were mixed so as to have the composition shown in the following Tables 3 to 5 B-2, Crosslinking agents C-1, C-2, C-3 as component (C), cyclopentanone (CP) as a solvent for component (D), E as an antioxidant for component (E) -1, E-2, after stirring and dissolving, it is finely filtered with a 0.2 μm filter made by Teflon (registered trademark) to prepare a photosensitive resin composition.

In Tables 3 to 5, photoacid generators B-1 and B-2, cross-linking agents C-1, C-2 and C-3, and antioxidants E-1 and E-2 are as follows.・Photo acid generator B-1:

・Photo acid generator B-2: CPI210S manufactured by SAN-APRO Co., Ltd.

・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 Using a spin coater, each photosensitive resin composition was coated on an 8-inch silicon wafer with a film thickness of 10 μm, and the aforementioned silicon wafer was primed with hexamethyldisilazane deal with. In order 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 it. For the obtained photosensitive resin film, in order to form a line and space pattern and a connection hole pattern, exposure was performed using a contact alignment type exposure device under 365 nm exposure conditions with a mask interposed therebetween. After light irradiation, PEB was performed on a hot plate at 120°C for 3 minutes. After cooling, the wafer was spray-developed with propylene glycol monomethyl ether acetate (PGMEA) for 300 seconds to form a pattern.

The photosensitive resin film on the patterned wafer formed by the aforementioned method is post-cured using an oven at 190°C for 2 hours while being diluted with nitrogen. After that, observe the formed connection hole pattern cross-sections of 50 μm, 30 μm, 20 μm, 10 μm, and 5 μm with a scanning electron microscope (SEM), and set the minimum hole pattern that penetrates and extends to the bottom of the film as Maximum resolution (maximum resolution). Furthermore, the verticality of the 50μm connecting hole pattern was evaluated from the obtained cross-sectional photos, the vertical pattern was evaluated as ◎, the slightly inverted tapered shape was evaluated as ○, and the inverted tapered shape was evaluated as △, The poor opening is evaluated as ×. The results are shown in Tables 6-8.

(3) Light transmittance test 1 Using a spin coater, each photosensitive resin composition was applied to an 8-inch glass wafer in a film thickness of 20 μm. In order to remove the solvent from the composition, the glass wafer was placed on a hot plate, heated at 110°C for 3 minutes, and dried. For the entire surface of the composition coated on the glass wafer, without a mask, use the mask aligner MA8 of SUSS MicroTec company to irradiate light with a high-pressure mercury lamp (wavelength 360nm) as the light source, and then perform PEB and immersion In PGMEA. The film remaining after this operation was further heated in an oven at 190°C for 2 hours to obtain a film. Using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.) for this coating, the transmittance of light with a wavelength of 405 nm was measured. The results are shown in Tables 9-11.

(4) Light transmittance test 2 A sample composed of a film on a glass wafer obtained by the same method as in (3) Light Transmittance Test 1 was continuously irradiated with a 405nm, 1W laser in an oven at 150°C, and the initial light transmittance was set It was 100%, and the change in light transmittance over time after 2,000 hours of irradiation at a wavelength of 405 nm was investigated. The results are shown in Tables 12-14.

(5) Evaluation of reliability (adhesion, crack resistance) The photosensitive resin film-coated wafer obtained by the same method as (3) Light Transmittance Test 1 was used with a dicing saw (DAD685, manufactured by DISCO Corporation, spindle rotation speed 40,000 rpm, cutting speed (20mm/sec) was cut to obtain a 10mm×10mm square test piece. The obtained test pieces (10 pieces each) were subjected to a thermal cycle test (maintained at -25°C for 10 minutes, held at 125°C for 10 minutes, and repeated 2,000 cycles) to confirm the peeling of the resin film from the wafer after the thermal cycle test State, whether there is cracking. The case where no peeling or cracking occurs at all is evaluated as "good"; the case where even one peeling occurs is evaluated as "peeling"; the case where even one crack occurs is evaluated as "cracking" . The results are shown in Tables 15-17.

From the above results, it can be seen that the photosensitive resin composition of the present invention can form fine patterns and exhibit sufficient characteristics as a photosensitive material. At the same time, the film has high light transmittance and good light resistance. And reliability (adhesion, crack resistance), so it is suitable as a material for optical semiconductor devices.

Claims (14)

A silicone polymer characterized in that the main chain contains a polysiloxane skeleton, a phenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton, and the side chain contains an epoxy group. The silicone polymer of claim 1, wherein a film with a thickness of 10 μm containing the aforementioned polymer has a transmittance of 97% or more of light with a wavelength of 405 nm. The silicone polymer of claim 1 or 2, which contains repeating units represented by the following formulas (A1) to (A4),

[In the formula, R ¹ to R ⁴ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms that may contain heteroatoms, and m is each independently an integer of 1 to 600. When m is an integer of 2 or more, each R ³ may They are the same or different from each other, each R ⁴ can be the same or different from each other, a ¹ , a ² , a ³ and a ⁴ are numbers satisfying the following formula: 0＜a ¹ ＜1, 0＜a ² ＜1 , 0＜a ³ ＜1, 0＜a ⁴ ＜1 and a ¹ + a ² + a ³ + a ⁴ =1, X ¹ is a divalent group represented by the following formula (X1), and X ² is the following The divalent group represented by 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 from 0 to 7, and R ¹³ is a divalent hydrocarbon group with 1 to 8 carbon atoms. Contains ester bond or ether bond)

(In the formula, R ²¹ and R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 8 carbon atoms, R ²³ and R ²⁴ are each independently a hydrogen atom or a methyl group, and p ¹ and p ² are each independently 1 to 6. Is an integer of 0~100)]. Such as the silicone polymer of claim 3, wherein q is an integer from 5 to 20. Such as the silicone polymer of claim 3, wherein m is an integer from 10 to 100. The silicone polymer of claim 3, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms. Such as the silicone polymer of claim 1, wherein the weight average molecular weight is 3,000 to 500,000. A photosensitive resin composition characterized by comprising (A) the silicone polymer of any one of claims 1 to 7 and (B) a photoacid generator. The photosensitive resin composition according to claim 8, wherein the content of the component (B) is 0.05 to 20 parts by mass relative to 100 parts by mass of the component (A). The photosensitive resin composition according to claim 8 or 9, which further contains (C) a cationically polymerizable crosslinking agent. The photosensitive resin composition according to claim 8 or 9, which further contains (D) a solvent. The photosensitive resin composition according to claim 8 or 9, which further contains (E) an antioxidant. A pattern forming method, which is characterized by including (i) The step of forming a photosensitive resin film on a substrate using the photosensitive resin composition of any one of claims 8 to 12, (ii) The step of exposing the aforementioned photosensitive resin film, and (iii) The step of developing the above-mentioned exposed photosensitive resin film using a developing solution. A method of manufacturing an optical semiconductor element provided with a photosensitive resin film, characterized by including the pattern forming method of claim 13.