JP2020094168A - Siloxane polymer containing isocyanuric acid skeleton and polyether skeleton, photosensitive resin composition, pattern forming method, and fabrication method of opto-semiconductor element - Google Patents

Abstract

To provide a novel polymer capable of giving a film having high transparency and high light resistance, a photosensitive resin composition capable of giving a film having high transparency, high light resistance and high heat resistance after patterned, while allowing formation of a fine pattern in a wide wavelength range, a pattern forming method using the photosensitive resin composition, and a fabrication method of an opto-semiconductor element.SOLUTION: A siloxane polymer is provided, which contains a polysiloxane skeleton, a silphenylene skeleton, an isocyanuric acid skeleton and a polyether skeleton in a main chain, and contains an epoxy group in a side chain. A photosensitive resin composition is provided, which comprises the above siloxane polymer and a photoacid generator.SELECTED DRAWING: None

Description

The present invention relates to a siloxane polymer having 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.

Up to now, an epoxy resin has been mainly used as a sealing protection material for various optical devices represented by a light emitting diode (LED), a CMOS image sensor and the like. Among them, many epoxy-modified silicone resins have been used as those having high transparency and light resistance, and there is also a type (patent document 1) in which an alicyclic epoxy group is introduced into a silphenylene skeleton.

Even if there is no problem with the conventional device in light resistance, the output power of optical devices such as LEDs has been increasing in recent years, so conventional sealing protective materials do not have sufficient light resistance, and gas emission, There was a problem such as discoloration. Further, in recent years, many optical devices require fine processing. When performing such fine processing, various resist materials typified by epoxy resin 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 a resist material, there is a type (patent document 2) in which an alicyclic epoxy modified silphenylene at both ends is introduced as a cross-linking agent, but when higher transparency is targeted, heat resistance However, the material is not sufficient in light resistance, and there has been a demand for a material capable of giving a film capable of withstanding more severe conditions.

Japanese Patent Publication No. 8-32763 JP 2012-001668 A

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

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a 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 is highly polymerized. Providing a transparent and highly light-resistant film, and the photosensitive resin composition containing the polymer and the photo-acid generator, while enabling fine pattern formation in a wide range of wavelengths, high transparency after pattern formation, The present invention has been completed by finding that a film having high light resistance and high heat resistance can be provided.

［式中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、ヘテロ原子を含んでいてもよい炭素数１〜２０の１価炭化水素基である。ｍは、それぞれ独立に、１〜６００の整数である。ｍが２以上の整数のとき、各Ｒ³は、互いに同一であっても異なっていてもよく、各Ｒ⁴は、互いに同一であっても異なっていてもよい。ａ¹、ａ²、ａ³及びａ⁴は、０＜ａ¹＜１、０＜ａ²＜１、０＜ａ³＜１、０＜ａ⁴＜１、及びａ¹＋ａ²＋ａ³＋ａ⁴＝１を満たす数である。Ｘ¹は、下記式（Ｘ１）で表される２価の基である。Ｘ²は、下記式（Ｘ２）で表される２価の基である。

（式中、Ｒ¹¹及びＲ¹²は、それぞれ独立に、水素原子又はメチル基である。ｎ¹及びｎ²は、それぞれ独立に、０〜７の整数である。Ｒ¹³は、炭素数１〜８の２価炭化水素基であり、その炭素原子間にエステル結合又はエーテル結合を含んでいてもよい。）

（式中、Ｒ²¹及びＲ²²は、それぞれ独立に、水素原子、又は炭素数１〜８の１価炭化水素基である。Ｒ²³及びＲ²⁴は、それぞれ独立に、水素原子又はメチル基である。ｐ¹及びｐ²は、それぞれ独立に、１〜６の整数である。ｑは、０〜１００の整数である。）］
４．ｑが、５〜２０の整数である３のシロキサンポリマー。
５．ｍが、１０〜１００の整数である３又は４のシロキサンポリマー。
６．Ｒ¹¹、Ｒ¹²、Ｒ²¹及びＲ²²が、水素原子である３〜５のいずれかのシロキサンポリマー。
７．重量平均分子量が３,０００〜５００,０００である１〜６のいずれかのシロキサンポリマー。
８．（Ａ）１〜７のいずれかのシロキサンポリマー及び（Ｂ）光酸発生剤を含む感光性樹脂組成物。
９．（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対し、０.０５〜２０質量部である８の感光性樹脂組成物。
１０．更に、（Ｃ）カチオン重合性架橋剤を含む８又は９の感光性樹脂組成物。
１１．更に、（Ｄ）溶剤を含む８〜１０のいずれかの感光性樹脂組成物。
１２．更に、（Ｅ）酸化防止剤を含む８〜１１のいずれかの感光性樹脂組成物。
１３．（ｉ）８〜１２のいずれかの感光性樹脂組成物を用いて基板上に感光性樹脂皮膜を形成する工程、
（ii）前記感光性樹脂皮膜を露光する工程、及び
（iii）前記露光した感光性樹脂皮膜を、現像液を用いて現像する工程
を含むパターン形成方法。
１４．１３のパターン形成方法を含む、感光性樹脂皮膜を備える光半導体素子の製造方法。 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. A siloxane polymer of 1, wherein the film having a thickness of 10 μm and made of the above polymer has a transmittance of light having a wavelength of 405 nm of 97% or more.
3. A siloxane polymer of 1 or 2 containing 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 having 1 to 20 carbon atoms and optionally containing a hetero atom. m is an integer of 1-600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. 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 ⁴ Is a number satisfying =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 carbon number of 1 to 1. 8 is a divalent hydrocarbon group and may contain an ester bond or an ether bond between its carbon atoms.)

(In the formula, 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, and q is an integer of 0 to 100.)]
4. A siloxane polymer of 3, wherein q is an integer from 5 to 20.
5. The siloxane polymer of 3 or 4, wherein m is an integer of 10 to 100.
6. The siloxane polymer according to any one of 3 to 5, wherein R ¹¹ , R ¹² , R ²¹ and R ²² are hydrogen atoms.
7. The siloxane polymer according to any one of 1 to 6 having a weight average molecular weight of 3,000 to 500,000.
8. A photosensitive resin composition comprising (A) a siloxane polymer of any one of 1 to 7 and (B) a photoacid generator.
9. 8. The photosensitive resin composition of 8, wherein the content of the component (B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the component (A).
10. Furthermore, the photosensitive resin composition of 8 or 9 containing (C) cationically polymerizable crosslinking agent.
11. Furthermore, the photosensitive resin composition in any one of 8-10 containing (D) solvent.
12. Furthermore, the photosensitive resin composition in any one of 8-11 containing (E) antioxidant.
13. (I) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of 8 to 12,
A pattern forming method comprising: (ii) exposing the photosensitive resin film to light; and (iii) developing the exposed photosensitive resin film using a developing solution.
14. A method for manufacturing an optical semiconductor device including a photosensitive resin film, including the pattern forming method according to 14.13.

The siloxane polymer of the present invention can be easily synthesized and can give a highly transparent and highly light-resistant film. Further, by using the photosensitive resin composition containing the polymer and the photo-acid generator, a film can be easily formed without being damaged by oxygen, and the film can be exposed to light having a wide wavelength, so that It is possible to form various patterns. Furthermore, the film 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 encapsulation of optical semiconductor elements and the like.

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

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

In formulas (A2) and (A4), R ^{1 to} R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom. m is an integer of 1-600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. When there are two or more siloxane units in the repeating units A2 and A4, all the siloxane units may be the same or may contain two or more different siloxane units. When two or more different siloxane units are contained (that is, when m is an integer of 2 or more), the siloxane units may be randomly bonded or alternately bonded, and include a plurality of blocks of the same siloxane unit. May be

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

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

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

Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group and a 4-tert-butyl group. Examples thereof include a phenyl group, a 4-butylphenyl group, a dimethylphenyl group, a naphthyl group, a biphenylyl group and a terphenylyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Further, the monovalent aromatic hydrocarbon group may contain a hetero atom, and specifically, a part or all of the hydrogen atoms of the monovalent aromatic hydrocarbon group have 1 to 10 carbon atoms. May be substituted with an alkoxy group of, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and 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. 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, nor Examples thereof include a bornyloxy group and an adamantyloxy group.

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, sec-butylthio group, tert-butylthio group. , Cyclobutylthio group, n-pentylthio group, cyclopentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n-decylthio group, norbornylthio group, adamantylthio group Groups and the like.

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

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, 4-ethylphenylthio group, 4-tert-butylphenylthio group, 4-butylphenylthio group, dimethylphenylthio group, naphthylthio group, biphenylylthio group, terphenylylthio group and the like can be mentioned.

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, Examples thereof include a 3-tert-butoxyphenyl group, a 4-tert-butoxyphenyl group, a biphenylyloxyphenyl group, and a biphenylylthiophenyl group.

1-10 are preferable and, as for carbon number of the said monovalent aliphatic hydrocarbon group, 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, as R ^{1 to} R ⁴ , a methyl group, an ethyl group, an n-propyl group or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable.

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

In the 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 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 and 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≦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 have 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, propane- Examples thereof include alkanediyl groups such as 1,2-diyl group, propane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group and the like. Be done. In addition, an ester bond or an ether bond may be present between the carbon atoms of the divalent hydrocarbon group. Of these, 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 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, preferably an integer of 1 to 4, and more preferably 1 or 2. Although q is an integer of 0 to 100, an integer of 1 to 50 is preferable, and an integer of 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 an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms. And other monovalent aliphatic hydrocarbon groups, aryl groups having 6 to 8 carbon atoms, and monovalent aromatic hydrocarbon groups such as aralkyl groups 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. , N-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and the like. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group and a pentenyl group.

Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group and a dimethylphenyl group. Can be mentioned. Examples of the aralkyl group include a benzyl group and a phenethyl group.

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 unit represented by the subscript q may be randomly bonded or alternately bonded, and may include a plurality of blocks of the same alkylene oxide unit.

The weight average molecular weight (Mw) of the siloxane polymer of the present invention is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. When the Mw is within the above range, the polymer can be obtained as a solid, and the film forming property can be secured. In the present invention, Mw is a polystyrene conversion measurement value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

The siloxane polymer of the present invention may have repeating units A1 to A4 randomly bonded or alternately bonded, and may have a plurality of blocks of each unit. In the siloxane polymer of the present invention, the content of siloxane units is preferably 10 to 90% by 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)). ), 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)), It can be produced by addition polymerization in the presence of a metal catalyst.

（式中、Ｒ¹〜Ｒ⁴、Ｒ¹¹〜Ｒ¹³、Ｒ²¹〜Ｒ²⁴、ｍ、ｎ¹、ｎ²、ｐ¹、ｐ²及びｑは、前記と同じ。）

(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 0 An integer of 6 to 6 is preferable, and 0 or 6 is particularly preferable.), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (for example, those described in US Pat. No. 3,220,972); Complexes of chloroplatinic acid with olefins (for example, those described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662, and U.S. Pat. No. 3,775,452); platinum group metals such as platinum black and palladium. Supported on a carrier such as alumina, silica, carbon; rhodium-olefin complex; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane ( In particular, a complex with a vinyl group-containing cyclic siloxane) or the like can be used.

The amount of the catalyst used is a catalytic amount, and it is generally preferable that the platinum group metal is 0.001 to 0.1 mass% in the total mass of the compounds (1) to (4).

In the polymerization reaction, a solvent may be used if necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferable. As the polymerization conditions, the polymerization temperature is, for example, 40 to 150° C., and particularly preferably 60 to 120° C., from the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time. Although the polymerization time depends on the kind and amount of the raw material compound, it is preferably completed in about 0.5 to 100 hours, particularly 0.5 to 30 hours in order to prevent moisture from intervening in the polymerization system. After the polymerization reaction is completed in this way, the above polymer can be obtained by distilling off a solvent, if used.

The reaction method is not particularly limited, but first, the compound (3) and the compound (4) are mixed and heated, then a metal catalyst is added to the mixed solution, and then the compound (1) and the compound (2) are added to 0. It is recommended to add it dropwise over 1 to 5 hours.

In each raw material compound, the molar ratio of the hydrosilyl group contained in the compound (1) and the compound (2) to the total of the alkenyl groups contained in the compound (3) and the compound (4) is preferably 0.67 to 1. 67, and more preferably 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 or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

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

[(B) Photo-acid generator]
The photoacid generator of the component (B) is not particularly limited as long as it decomposes by irradiation with light to generate an acid, but one generating an acid by irradiation with light having a wavelength of 190 to 500 nm is preferable. The photoacid generator (B) is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oximesulfonate derivatives, iminosulfonates. Examples thereof include derivatives and triazine derivatives.

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

In formulas (B1) and (B2), R ^{101 to} R ¹⁰⁵ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent, and a carbon number which may have a substituent. It is an aryl group having 6 to 12 or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. A ^- is a non-nucleophilic counterion.

The alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group. Group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the substituent include an oxo group, a linear, branched or cyclic C1-C12 alkoxy group, a linear, branched or cyclic C1-C12 alkyl group, and a carbon number 6-24. And aryl groups of 7 to 25 carbon atoms, aryloxy groups of 6 to 24 carbon atoms, arylthio groups of 6 to 24 carbon atoms, and the like.

As R ^{101 to} R ¹⁰⁵ , an alkyl group which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and a 2-oxocyclohexyl group; a 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, Aryl group which may have a substituent such as 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group, terphenylyl group, biphenylyloxyphenyl group, biphenylylthiophenyl group; benzyl group, phenethyl group An aralkyl group which may have a substituent such as a 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 ion such as chloride ion and bromide ion; triflate ion, fluoroalkanesulfonate ion such as 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; Aryl sulfonate ion such as rate ion, benzene sulfonate ion, 4-fluorobenzene sulfonate ion, 1,2,3,4,5-pentafluorobenzene sulfonate ion; alkane sulfonate ion such as mesylate ion, butane sulfonate ion; trifluoromethane Fluoroalkanesulfonimide ion such as sulfonimide ion; Fluoroalkanesulfonylmethide ion such as tris(trifluoromethanesulfonyl)methide ion; Tetrakisphenyl borate ion, borate ion such as tetrakis(pentafluorophenyl)borate ion, etc.

Examples of the diazomethane derivative include compounds represented by the following formula (B3).

In formula (B3), R ¹¹¹ and R ¹¹² each independently represent 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 It is an aralkyl group having 7 to 12 carbon atoms.

Examples of the alkyl group are the same as those exemplified in the description of R ^{101 to} R ¹⁰⁵ . Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group and a nonafluorobutyl group.

The aryl group which may have a substituent is a phenyl group; a 2-, 3- or 4-methoxyphenyl group, a 2-, 3- or 4-ethoxyphenyl group, a 3- or 4-tert-butoxy group. Alkoxyphenyl group such as phenyl group; 2-, 3- or 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, alkylphenyl group such as dimethylphenyl group; fluorophenyl group And halogenated aryl groups such as chlorophenyl group and 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Examples of the glyoxime derivative include compounds represented by the following formula (B4).

In formula (B4), R ^{121 to} R ¹²⁴ each independently represent 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 It is an aralkyl group having 7 to 12 carbon atoms. R ¹²³ and R ¹²⁴ may be bonded to each other to form a ring together with the carbon atom to which they are bonded. When forming a ring, the group formed by R ¹²³ and R ¹²⁴ being bonded is It is a linear or branched alkylene group having 1 to 12 carbon atoms.

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

Specific examples of the onium salts include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-tert-butoxy). Phenyl)phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl)diphenylsulfonium, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate tris( p-tert-butoxyphenyl)sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl)diphenylsulfonium, p-toluenesulfonate bis(p-tert-butoxyphenyl)phenylsulfonium , Tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, trifluoromethane Cyclohexylmethyl(2-oxocyclohexyl)sulfonium sulfonate, Cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, Dimethylphenylsulfonium trifluoromethanesulfonate, Dimethylphenylsulfonium p-toluenesulfonate, Dicyclohexylphenyltrifluoromethanesulfonate Sulfonium, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl ]-4-Biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, trikis(fluorophenyl)borate triphenylsulfonium, tetrakis(fluorophenyl)borate tris[4-(4-acetylphenyl)thiophenyl]sulfonium, tetrakis( Pentafluorophenyl)borate triphenylsulfonium And tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

Specific examples of the diazomethane derivative include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, 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(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1- Examples thereof include cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

Specific examples of the glyoxime derivative include 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-pentane Dione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α -Dicyclohexyl glyoxime, 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-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α- Dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl) Examples include -α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

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

Specific examples of the disulfone derivative include diphenyldisulfone and dicyclohexyldisulfone.

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

Specific examples of the sulfonic acid ester derivative include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p- Examples include toluenesulfonyloxy)benzene and the like.

Specific examples of the imido-yl-sulfonate derivative include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate and 5-norbornene-2,3. -Dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butyl sulfonate, n-trifluoromethylsulfonyloxynaphthylimide and the like.

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

Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methyl Phenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile and the like.

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

As the photoacid generator as 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, and 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 can be easily obtained, and the curability in a thick film can be effectively prevented from being deteriorated by the light absorption of the photoacid generator itself. be able to. In order to obtain the transparency and light resistance which are the features of the present invention, it is preferable that the amount of the photo-acid generator as the component (B) having a light-absorbing property is small as long as the photo-curability is not impaired. The photo-acid generator as the component (B) may be used alone or in combination of two or more.

[(C) Cationic Polymerizable Crosslinking Agent]
The photosensitive resin composition of the present invention may further contain a cationically polymerizable crosslinking agent as the component (C). The cationic polymerizable cross-linking agent is capable of causing a cationic polymerization reaction with the epoxy group of the component (A), is a component for easily forming a pattern, and further enhances the strength of the resin film after photocuring. To raise.

The crosslinking agent is preferably a compound having a molecular weight of 100 to 15,000, more preferably a compound having a molecular weight of 200 to 1,000. When the molecular weight is 100 or more, sufficient photocurability can be obtained, and when it is 15,000 or less, the heat resistance of the composition after photocuring is not deteriorated, which is preferable. The compound may be a resin (polymer), in which case the molecular weight is the weight average molecular weight (Mw).

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

The content of the component (C) is 0 to 100 parts by mass with respect to 100 parts by mass of the component (A), but when contained, it is preferably 0.5 to 100 parts by mass, and 0.5 to 60 parts by mass. Is more preferable and 1 to 50 parts by mass is further preferable. When the content of the component (C) is 0.5 parts by mass or more, sufficient curability is obtained upon irradiation with light, and when it is 100 parts by mass or less, the proportion of the component (A) in the photosensitive resin composition is Since it does not decrease, the cured product can sufficiently exhibit the effect of the present invention. As the component (C), one type can be used alone, or two or more types can be used in combination.

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

As the solvent (D), an organic solvent is preferable, and specific examples thereof 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 monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Ethers of 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-propionate. Examples thereof include esters such as butyl, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone. These may be used alone or in combination of two or more.

As the solvent (D), ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and a mixed solvent thereof are particularly preferable because they have excellent photoacid generator solubility.

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

[(E) Antioxidant]
The photosensitive resin composition of the present invention may contain an antioxidant as an additive. By containing an antioxidant, heat resistance can be improved. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds.

The hindered phenol compound is not particularly limited, but the following compounds are preferable. 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'-Methylenebis(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) (Brand name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (Brand name: Nocrac NS-5), 4,4'-butylidene bis(3-methyl-6-tert- Butylphenol) (trade name: ADEKA STAB AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate (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: Synox 226M), 4,6-bis(octylthio) Methyl)-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: ADEKA STAB AO-30), tetrakis[methylene -(3,5-di-tert-butyl-4-hydroxy Hydrocinnamate)] methane (trade name: ADEKA STAB 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'-hexa Methylenebis(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-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-tetra Oxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3, Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium/polyethylene wax mixture (50:50) (trade 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]dioxaphosphepine (trade name: Sumilizer GP) and the like.

The hindered amine compound is not particularly limited, but the following compounds are preferable. For example, p,p'-dioctyldiphenylamine (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'-di-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-toluenesulfonylaminodiphenylamine (trade name) : Nocrac TD), N-phenyl-N'-(3-methacryloyloxy-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-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl succinate Piperidine 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]] (trade 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-Butane tetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (trade name) : LA-52), a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62 ) 1,2,3,4-butanetetracarboxylic acid and a mixed esterified product of 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), 1,2 ,3,4-Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8, Mixed esterified product with 10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4 -Piperidinol and mixed esterified product with 3,9-bis(2-hydroxy-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: ADEKA STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl) )-2-Propylenecarboxylate (trade name: ADEKA STAB LA-87) and the like.

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

[Other additives]
The photosensitive resin composition of the present invention may contain other additives in addition to the components described above. Examples of the additives include surfactants that are commonly used to improve coatability.

The surfactant is preferably a nonionic one, for example, a fluorine-based surfactant, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane. System compounds and the like. These may be commercially available products, for example, Fluorad (registered trademark) FC-430 (manufactured by 3M), Surflon (registered trademark) S-141 and S-145 (manufactured by AGC Seimi Chemical Co., Ltd.). ), Unidyne (registered trademark) DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) F-8151 (manufactured by DIC Corporation), X-70-093 ( Shin-Etsu Chemical Co., Ltd.) and the like. Among these, Fluorad FC-430 and X-70-093 are preferable. The content of the surfactant is not particularly limited as long as the effect of the present invention is not impaired, but when it is contained, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

Also, a silane coupling agent can be used as an additive. By including the silane coupling agent, the adhesion of the photosensitive resin composition to the adherend can be further enhanced. Examples of the silane coupling agent include epoxy silane coupling agents and aromatic-containing aminosilane coupling agents. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited as long as the effect of the present invention is not impaired, but when it is contained, it is preferably 0.01 to 5 mass% 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 in which the above components are stirred and mixed, and then filtered with a filter or the like to remove solids as necessary.

[Pattern formation method]
The pattern forming method of the present invention uses the photosensitive resin composition,
(I) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition described above,
The method includes the step of (ii) exposing the photosensitive resin film to light, and (iii) developing the exposed photosensitive resin film using a developing solution. A fine pattern can be obtained by this method.

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

The photosensitive resin film can be formed by a known method. For example, it can be formed by applying the photosensitive resin composition onto a substrate by a method such as a dipping method, a spin coating method or a roll coating method. The coating amount can be appropriately selected according to the purpose, but is preferably an amount such that the film thickness is 0.1 to 100 μm.

Here, in order to efficiently perform the photo-curing reaction, the solvent or the like may be pre-evaporated by preliminary heating, if necessary. The preheating can be performed, for example, at 40 to 160° C. for about 1 minute to 1 hour.

Next, in 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 having various wavelengths generated by a radiation generator, for example, ultraviolet rays such as g-rays and i-rays, far ultraviolet rays (248 nm), and the like. The exposure amount is preferably 10 to 5,000 mJ/cm ² .

The exposure may be performed via a photomask. The photomask may be, for example, one having a desired pattern cut through. The material of the photomask is preferably one that shields the light having the wavelength of 240 to 500 nm, and chrome or the like is preferably used, but the material is not limited to this.

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

Step (iii) is a step of developing the photosensitive resin film with a developing solution after exposure or after PEB. The developer is preferably an organic solvent-based developer used as a solvent, for example, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or the like. By developing with the organic solvent-based developer, a negative pattern in which the non-exposed area is dissolved and removed can be obtained. The development can be performed by an ordinary method, for example, by immersing the substrate on which the pattern is formed in the developing solution. Then, if necessary, washing, rinsing, drying, etc. are performed to obtain a film having a desired pattern.

Although the method for forming the pattern is as described above, when it is not necessary to form the pattern, for example, when it is desired to form a simple uniform film, in the step (ii) in the pattern forming method, the photomask is not used. Instead, the film may be formed by exposure to light having an appropriate wavelength.

Further, if necessary, (iv) the film on which the pattern is formed is further heated at 120 to 300° C. for about 10 minutes to 10 hours by using an oven or a hot plate to increase the crosslink density and to evaporate remaining volatilization. You may perform the process (post-curing) which removes a component.

[Optical semiconductor element]
An optical semiconductor element can be manufactured by forming a fine pattern by the above method using the photosensitive resin composition. A film obtained from the photosensitive resin composition is excellent in transparency, light resistance and heat resistance, and an optical semiconductor device provided with the film is a light emitting device such as a light emitting diode, a photodiode, an optical sensor, a CMOS image sensor. It is preferably used for optical devices such as light receiving elements such as, and optical transmission devices such as optical waveguides. The film has a transmittance of light having a wavelength of 405 nm of preferably 92% or more, more preferably 96% or more, and particularly preferably 98% or more.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following Examples, Mw was a monodisperse dispersion under the analysis conditions of TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column, a flow rate of 0.6 mL/min, an elution solvent of THF, and a column temperature of 40°C. It was measured by GPC using polystyrene as a standard.

The compounds (S-1), (S-2a), (S-2b), (S-3a), (S-3b), (S-4), (S-5) and (S-1) used in the synthesis of the polymer. S-6) is as follows.

[1] Synthesis of polymer and its evaluation (1) Synthesis of polymer [Example 1-1] Synthesis of polymer 1 The compound (S-4) was placed in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser. After 132.5 g (0.50 mol) and 269.5 g (0.50 mol) of the compound (S-3a) were added, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 116.4 g (0.60 mol) of compound (S-1) and 1,208.0 g of compound (S-2a). (0.40 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 1 (siloxane unit content rate: 70.0 mass %). The Mw of polymer 1 was 43,000. The polymer 1 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-2] Synthesis of polymer 2 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 79.5 g (0.30 mol) of compound (S-4) and compound (S-) were mixed. After 37.3 g (0.70 mol) of 3a) was added, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0) of compound (S-2b). (10 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 2 (siloxane unit content: 20.1% by mass). The Mw of polymer 2 was 83,000. The polymer 2 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-3] Synthesis of polymer 3 26.5 g (0.10 mol) of compound (S-4) and compound (S-) were placed in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser. After 485.1 g (0.90 mol) of 3a) was added, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 135.8 g (0.70 mol) of the compound (S-1) and 475.5 g (0 of the compound (S-2b)). (0.30 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 3 (siloxane unit content rate: 42.3% by mass). The Mw of polymer 3 was 8,000. The polymer 3 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-4] Synthesis of polymer 4 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 238.5 g (0.90 mol) of compound (S-4) and compound (S-) were added. After adding 53.9 g (0.10 mol) of 3a), 2,000 g of toluene was added and heated to 70°C. Then, 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 of compound (S-2a)). (.20 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 4 (siloxane unit content rate: 57.4% by mass). The Mw of polymer 4 was 143,000. The polymer 4 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-5] Synthesis of polymer 5 185.5 g (0.70 mol) of compound (S-4) and compound (S-) were placed in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser. 3b) After adding 254.5 g (0.30 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 77.6 g (0.40 mol) of the compound (S-1) and 951.0 g (0 of the compound (S-2b)). (60 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 5 (siloxane unit content rate: 65.2 mass %). The Mw of polymer 5 was 23,000. The polymer 5 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Example 1-6] Synthesis of polymer 6 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser, 132.5 g (0.50 mol) of compound (S-4) and compound (S-) were added. 3b) 409.0 g (0.50 mol) was added, then 2,000 g of toluene was added, and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0) of compound (S-2a). (10 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a polymer 6 (siloxane unit content rate: 29.7 mass %). The Mw of polymer 6 was 103,000. The polymer 6 was confirmed to be a polymer containing repeating units A1 to A4 by ¹ H-NMR (manufactured by Bruker).

[Comparative Example 1-1] Synthesis of Comparative Polymer 1 A compound (S-4) 212.0 g (0.80 mol) and compound (S) were placed in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser. -6) After adding 86.0 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 184.3 g (0.95 mol) of the compound (S-1) and 79.3 g (0) of the compound (S-2b). 0.05 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 1 (siloxane 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 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser, 212.0 g (0.80 mol) of compound (S-4) and compound (S) were added. -5) After 78.4 g (0.20 mol) was added, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 38.8 g (0.20 mol) of compound (S-1) and 1,268.0 g of compound (S-2b). (0.80 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure 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 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 431.2 g (0.80 mol) of compound (S-3a) and compound (S). -6) After adding 86.0 g (0.20 mol), 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 158.5 g (0) of compound (S-2b). (10 mol) was added dropwise over 1 hour (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 from the reaction solution under reduced pressure to obtain Comparative Polymer 3 (siloxane unit content rate: 18.6% by mass). The Mw of comparative polymer 3 was 28,000.

[Comparative Example 1-4] Synthesis of Comparative Polymer 4 In a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser, 654.4 g (0.80 mol) of compound (S-3b) and compound (S). -5) After 78.4 g (0.20 mol) was added, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0) of compound (S-2a). (10 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure 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 5 215.0 g (0.50 mol) of compound (S-6) and compound (S) were placed in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser. -5) After adding 196.0 g (0.50 mol), 2,000 g of toluene was added and the mixture was heated to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 135.8 g (0.70 mol) of compound (S-1) and 906.0 g (0) of compound (S-2a). (0.30 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 5 (siloxane 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 adding 430.0 g (1.00 mol) of the compound (S-6) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device and a reflux condenser. Toluene (2,000 g) was added, and the mixture was heated to 70°C. Then, 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 of compound (S-2a)). (.20 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a comparative polymer 6 (siloxane unit content rate: 50.8 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 the compound (S-5) to a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device and a reflux condenser. Toluene (2,000 g) was added, and the mixture was heated to 70°C. Then, 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 of compound (S-2a)). (.20 mol) was added dropwise over 1 hour (total of hydrosilyl groups/total of alkenyl groups=1/1 (molar ratio)). After completion of the dropping, the mixture was heated to 100° C. and aged for 6 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain Comparative Polymer 7 (siloxane unit content rate: 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 displacement device and a reflux condenser, Toluene (2,000 g) was added, and the mixture was heated to 70°C. Then, 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 of compound (S-2a)). (.20 mol) was added dropwise over 1 hour (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 from the reaction solution under reduced pressure to obtain Comparative Polymer 8 (siloxane unit content 59.0 mass %). The Mw of comparative polymer 8 was 70,000.

(2) Light transmission test [Examples 2-1 to 2-6]
Each of Polymers 1 to 6 was dissolved in cyclopentanone to a concentration of 50% by mass to prepare a resin solution. Each resin solution was applied onto a glass wafer, and heated at 60° C. for 30 minutes and at 190° C. for 2 hours in a nitrogen atmosphere to form a resin film (thickness 10 μm). The light transmittance of the obtained film at a wavelength of 405 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Table 1.

The sample consisting of the film on the glass wafer obtained by the above method was irradiated with a laser having a wavelength of 405 nm and 1 W for 100 hours in an oven at 50° C. and the light transmittance after irradiation for 1,000 hours. The transmittance was measured. The results are shown in Table 2.

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

[2] Preparation of photosensitive resin composition and its evaluation [Examples 3-1 to 3-10, Comparative examples 2-1 to 2-19]
(1) Preparation of Photosensitive Resin Composition Polymers 1 to 6 as the component (A), comparative polymers 1 to 8 and a photo-acid generator B as the component (B) so as to have the compositions shown in Tables 3 to 5 below. -1, B-2, cross-linking agent as component (C) C-1, C-2, C-3, cyclopentanone (CP) as solvent for component (D), and E as antioxidant for component (E) -1, E-2 were mixed, stirred and dissolved, and then microfiltered with a Teflon (registered trademark) 0.2 μm filter to prepare a photosensitive resin composition.

In Tables 3 to 5, photoacid 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. ..
-Photo acid generator B-1:

Photo acid generator B-2: CPI210S manufactured by San-Apro Co., Ltd.

-Crosslinking agents C-1, C-2, C-3:

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

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

(2) Evaluation of Pattern Formation Each photosensitive resin composition was coated on an 8-inch silicon wafer primed with hexamethyldisilazane with a film thickness of 10 μm using a spin coater. To remove the solvent from the composition, the wafer was placed on a hot plate, heated at 110° C. for 3 minutes and dried. The obtained photosensitive resin film was exposed through a mask to form a line-and-space pattern and a contact hole pattern using a contact aligner type exposure device under an exposure condition of 365 nm. After the light irradiation, PEB was performed at 120° C. for 3 minutes on a hot plate and then cooled, and 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 wafer having the pattern formed by the above method was post-cured in an oven at 190° C. for 2 hours while purging with nitrogen. Then, using a scanning electron microscope (SEM), observe the cross section of the formed 50 μm, 30 μm, 20 μm, 10 μm, 5 μm contact hole pattern, and determine the minimum hole pattern where the holes penetrate to the bottom of the film. And Further, the verticality of the contact hole pattern of 50 μm was evaluated from the obtained cross-sectional photograph, and the vertical pattern was marked with ⊚, the reverse taper shape was marked with ◯, the reverse taper shape was marked with Δ, and the opening defect was marked with x. The results are shown in Tables 6-8.

(3) Light transmission test 1
Each photosensitive resin composition was coated on an 8-inch glass wafer 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, heated at 110° C. for 3 minutes and dried. The entire surface of the composition coated on the glass wafer was irradiated with light from a high pressure mercury lamp (wavelength 360 nm) as a light source using a mask aligner MA8 of SUSS MICROTEC Co., Ltd. without using a mask, and then PEB was performed to perform PGMEA. Soaked in. The film remaining after this operation was further heated in an oven at 190° C. for 2 hours to obtain a film. The transmittance of light having a wavelength of 405 nm was measured for this film using a spectrophotometer U-3900H (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in Tables 9-11.

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

(5) Evaluation of reliability (adhesiveness, crack resistance) (3) Dicing saw equipped with dicing blade (DAD685, manufactured by DISCO) The spindle rotation speed was 40,000 rpm, and the cutting speed was 20 mm/sec) to obtain a 10 mm×10 mm square test piece. The obtained test pieces (10 pieces each) were subjected to a heat cycle test (holding at −25° C. for 10 minutes and holding at 125° C. for 10 minutes was repeated 2,000 cycles) to obtain a resin film after the heat cycle test. The state of peeling from the wafer and the presence or absence of cracks were confirmed. Those free from peeling/cracking were evaluated as good, those in which even one peeled were peeled, and those in which even one cracked were regarded as cracks. The results are shown in Tables 15-17.

From the above results, the photosensitive resin composition of the present invention is capable of forming a fine pattern, and exhibits sufficient characteristics as a photosensitive material, and its film has high light transmittance, and good light resistance and reliability. It has been found that it has properties (adhesion and crack resistance) and is useful as a material for optical semiconductor devices.

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 film made of the polymer and having a thickness of 10 μm has a transmittance of light having a wavelength of 405 nm of 97% or more. The siloxane polymer according to claim 1 or 2, comprising a repeating unit represented by the following formulas (A1) to (A4).

[In the formula, R ^{1 to} R ⁴ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom. m is an integer of 1-600 each independently. When m is an integer of 2 or more, each R ³ may be the same or different, and each R ⁴ may be the same or different. 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 ⁴ Is a number satisfying =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 carbon number of 1 to 1. 8 is a divalent hydrocarbon group and may contain an ester bond or an ether bond between its carbon atoms.)

(In the formula, 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, and q is an integer of 0 to 100.)] The siloxane polymer according to claim 3, wherein q is an integer of 5 to 20. The siloxane polymer according to claim 3 or 4, 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 any one of claims 1 to 6, having a weight average molecular weight of 3,000 to 500,000. A photosensitive resin composition comprising (A) the siloxane polymer according to 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 with respect to 100 parts by mass of the component (A). The photosensitive resin composition according to claim 8 or 9, further comprising (C) a cationically polymerizable crosslinking agent. The photosensitive resin composition according to claim 8, further comprising (D) a solvent. Furthermore, the photosensitive resin composition of any one of Claims 8-11 containing (E) antioxidant. (I) a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition according to any one of claims 8 to 12,
A pattern forming method comprising: (ii) exposing the photosensitive resin film to light; and (iii) developing the exposed photosensitive resin film using a developing solution. A method for manufacturing an optical semiconductor element comprising a photosensitive resin film, comprising the pattern forming method according to claim 13.