Polymers containing a silylphenyl backbone, photosensitive resin compositions, pattern forming methods, and methods for manufacturing optical semiconductor devices.

Abstract

The present invention provides a polymer having a main chain comprising a silylphenyl backbone, an isocyanuric acid backbone and a hydroxy-substituted alkyl ether backbone, and an epoxy group in the side chain.

Description

Technical Field

[0001] This invention relates to a polymer containing a silylphenyl backbone, a photosensitive resin composition, a pattern forming method, and a method for manufacturing an optical semiconductor device. Prior Technology

[0002] Traditionally, transparent epoxy resin has been used as an encapsulation and adhesive in various optical devices, such as light-emitting diodes (LEDs) and CMOS image sensors. In recent years, due to the frequent need for microfabrication in various optical devices, epoxy resin-based resist materials have been widely used.

[0003] In recent years, optical devices such as LEDs have made continuous progress in increasing their output. While being able to be microfabricated, higher transparency and lightfastness are required than ever before in order to suppress gas generation and discoloration. As a microfabricable material with particularly high transparency or lightfastness, examples include photosensitive materials using epoxy-modified polysiloxane resins with an incorporation of isocyanuric acid and norbornene backbone (Patent Document 1).

[0004] Recently, for such photosensitive materials, in addition to transparency and lightfastness, there is a demand for further improvements in properties, especially the ability to cure at low temperatures. However, the aforementioned epoxy-modified polysiloxane resin is not a material that can be cured at a low temperature of 130°C. Therefore, it is desirable to use photosensitive materials that possess not only epoxy groups but also other highly reactive functional groups. Introducing other highly reactive functional groups into epoxy resins not only makes low-temperature curing possible but also is expected to contribute to improved processability. Therefore, it becomes a high-value-added material that can be microprocessed and cured at low temperatures. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-90649 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] The present invention has been made in view of the above circumstances, and its object is to provide a polymer that can form fine patterns at a wide range of wavelengths, can be cured at low temperatures, and has a film with high transparency and high light resistance, a photosensitive resin composition containing the polymer, a pattern forming method using the photosensitive resin composition, and a method for manufacturing a semiconductor element. [Means for Solving the Problems]

[0008] As a result of repeated studies by the present inventors to achieve the above object, it was found that a polymer having a silylenephenylene skeleton, an isocyanuric acid skeleton, and a hydroxy-substituted alkyl ether skeleton in the main chain and an epoxy group in the side chain provides a film that can be cured at low temperatures and has high transparency and high light resistance, and a photosensitive resin composition containing the polymer of the present invention can provide a film that can form fine patterns at a wide range of wavelengths, can be cured at low temperatures, and has high transparency and high light resistance, and thus the present invention was completed.

[0009] That is, the present invention provides the following polymer containing a silylenephenylene skeleton, a photosensitive resin composition, a pattern forming method, and a method for manufacturing an optical semiconductor element. 1. A polymer having a silylenephenylene skeleton, an isocyanuric acid skeleton, and a hydroxy-substituted alkyl ether skeleton in the main chain and an epoxy group in the side chain. 2. The polymer according to 1, wherein the carbon number of the hydroxy-substituted alkyl ether skeleton is 9 to 20. 3. The polymer according to 1 or 2, which contains a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2), and a repeating unit represented by the following formula (A3). (In the formula, a, b, and c are positive numbers satisfying 0 < a < 1, 0 ≤ b < 1, 0 < c < 1, and a + b + c = 1. X1 is a divalent group represented by the following formula (X1). X2 is a divalent group represented by the following formula (X2). X3 is a divalent group represented by the following formula (X3).) (In the formula, R11 and R12 are each independently a hydrogen atom or a methyl group. R13 is a hydrocarbon group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be interposed between the carbon-carbon bonds. n1 and n2 are each independently an integer of 0 to 7. The dotted line is a bonding bond.) (In the formula, R 21 and R 22 are each independently a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. m is an integer of 0 to 10. The dashed line is a bonding bond.) (In the formula, R 31 and R 32 are each independently a hydrogen atom or a methyl group. R 33 is a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. When R 33 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent. R 34 is a hydroxyl group or a saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. When R 34 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent. When R 33 is a hydrogen atom and R 34 is a saturated hydrocarbon group, R 34 contains at least one primary or secondary alcoholic hydroxyl group as a substituent. When R 33 and R 34 are both saturated hydrocarbon groups, at least one primary or secondary alcoholic hydroxyl group is contained as a substituent in one or both of them. p 1 and p 2 are each independently an integer of 1 to 7. q 1 and q 2 are each independently an integer of 1 to​​​​​​​​​​​​​​​​​​​​​​​​​13. A method for manufacturing an optical semiconductor device having a photosensitive resin film, which includes the patterning method as described in 12. [Effects of the Invention]

[0010] The polymer of the present invention can be cured at a low temperature, particularly at a low temperature of 130°C or lower, and can provide a film having high transparency and high light resistance. The polymer of the present invention can be synthesized simply. Also, by using the photosensitive resin composition containing the polymer of the present invention, fine patterns can be formed using light of a wide range of wavelengths. In addition, the film obtained from the photosensitive resin composition of the present invention has excellent transparency and light resistance, can be cured at a low temperature of 130°C or lower, and can be suitably used for the protection and encapsulation of optical semiconductor devices. Embodiments

[0011] [Polymer Containing a Silicon Phenylene Skeleton]

[0012] The polymer of the present invention is a polymer having a silicon phenylene skeleton, an isocyanuric acid skeleton, and a hydroxy-substituted alkyl ether skeleton in the main chain, and an epoxy group in the side chain. The carbon number of the hydroxy-substituted alkyl ether skeleton is preferably 9 to 20. The aforementioned polymer may further include a norbornene skeleton in the main chain.

[0013] As such a polymer, it is preferably a polymer containing a repeating unit represented by the following formula (A1), a repeating unit represented by the following formula (A2), and a repeating unit represented by the following formula (A3).

[0014] In formulas (A1) to (A3), a, b, and c are positive numbers satisfying 0 < a < 1, 0 ≤ b < 1, 0 < c < 1, and a + b + c = 1.

[0015] In formula (A1), X1 is a divalent group represented by the following formula (X1). The divalent group represented by the following formula (X1) is a group having an isocyanuric acid skeleton. (The dotted line is a bonding bond.)

[0016] In formula (X), R11 and R12 are each independently a hydrogen atom or a methyl group.

[0017] In formula (X1), R13 is an alkyl group with 1 to 8 carbon atoms, and ester or ether bonds may exist between the carbon-carbon bonds. The alkyl group represented by R13 can be linear, branched, or cyclic. Specific examples include alkyl dimethyl groups such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl. Among these, methylene or ethyl groups are preferred as R13, with methylene groups being more preferred. Furthermore, ester or ether bonds may exist between the carbon-carbon bonds of the aforementioned alkyl groups.

[0018] In equation (X1), n1 and n2 are each an independent integer from 0 to 7.

[0019] In formula (A2), X2 is a divalent group represented by the following formula (X2). The divalent group represented by the following formula (X2) is a group having a norundinene skeleton. (The dashed lines represent the bond.)

[0020] In formula (X2), R21 and R22 are each independently a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. The aforementioned saturated hydrocarbon group can be any of linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Furthermore, the aforementioned saturated hydrocarbon groups may also contain heteroatoms. Specifically, some or all of the hydrogen atoms in the aforementioned saturated hydrocarbon groups may be replaced by halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, and carbonyl groups, ether bonds, thioether bonds, etc. may also be located between carbon atoms.

[0021] In equation (X2), m is an integer from 0 to 10, but preferably 0.

[0022] In formula (A3), X3 is a divalent group represented by the following formula (X3). The divalent group represented by the following formula (X3) is a group having a hydroxyl-substituted alkyl ether skeleton. (The dashed lines represent the bond.)

[0023] In formula (X3), R31 and R32 are each independently a hydrogen atom or a methyl group, but preferably a hydrogen atom.

[0024] In formula (X3), R33 is a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When R33 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent. R34 is a hydroxyl group or a saturated hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When R34 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent. The saturated hydrocarbon groups represented by R33 and R34 can be any of the following: linear, branched, or cyclic. As specific examples, examples identical to those exemplified in the description of formula (X2) as saturated hydrocarbon groups represented by R21 and R22 can be given. Furthermore, the aforementioned saturated hydrocarbon groups may also contain heteroatoms. Specifically, some or all of the hydrogen atoms in the aforementioned saturated hydrocarbon groups may be replaced by halogen atoms such as fluorine, chlorine, bromine, and iodine atoms, and carbonyl groups, ether bonds, thioether bonds, etc. may also be located between carbon atoms.

[0025] When R33 is a hydrogen atom and R34 is a saturated hydrocarbon group, R34 contains at least one primary or secondary alcoholic hydroxyl group as a substituent. When both R33 and R34 are saturated hydrocarbon groups, one or both contain at least one primary or secondary alcoholic hydroxyl group as a substituent. In the case where R33 and R34 contain alcoholic hydroxyl groups, it is preferable that R33 and R34 are straight-chain alkyl groups with a primary alcoholic hydroxyl group at the end.

[0026] In formula (X3), p1 and p2 are each independent integers from 1 to 7, but preferably 1. q1 and q2 are each independent integers from 1 to 7, but preferably 1. The number of carbon atoms contained in the divalent radical represented by formula (X3) is preferably 9 to 20.

[0027] The polymer of this invention is preferably of a weight-average molecular weight (Mw) of 3,000 to 500,000, and more preferably of 5,000 to 200,000. If Mw is within the aforementioned range, the polymer can be obtained as a solid, and film-forming properties can also be ensured. Furthermore, in this invention, Mw is a polystyrene-converted value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the dissolution solvent.

[0028] The polymer of the present invention may be a random copolymer of repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3), or an alternating copolymer, or a block copolymer containing plural units of each type.

[0029] In the polymer of the present invention, a, b, and c in formula (1) are positive numbers satisfying 0 < a < 1, 0 ≤ b < 1, 0 < c < 1, and a + b + c = 1. Preferably, 0 < a < 1, 0 < b < 1, 0 < c < 1. More preferably, 0.1 < a < 0.8, 0.1 < b < 0.8, 0.1 < c < 0.8. Even more preferably, 0.15 < a < 0.65, 0.15 < b < 0.65, 0.15 < c < 0.65.

[0030] <000013�>[Method for Producing Polymer Containing Silicon Phenylene Skeleton] The aforementioned polymer can be produced by subjecting a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (4), and, if necessary, a compound represented by the following formula (3) to addition polymerization in the presence of a metal catalyst.

[0031] (In the formula, R11 to R13, n1, and n2 are the same as described above.)

[0032] (In the formula, R21, R22, and m are the same as described above.)

[0033] (In the formula, R31 to R34, p1, p2, q1, and q2 are the same as described above.)

[0034] As the aforementioned metal catalyst, platinum group metal monomers such as platinum (including platinum black), rhodium, and palladium can be used; H₂PtCl₄·xH₂O, H₂PtCl₆·xH₂O, NaHPtCl₆·xH₂O, KHPtCl₆·xH₂O, Na₂PtCl₆·xH₂O, K₂PtCl₄·xH₂O, PtCl₄·xH₂O, PtCl₂, Na₂HPtCl₄·xH₂O Platinum chloride, chloroplatinic acid, and chloroplatinate, etc. (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6). Alcohol-modified chloroplatinic acid (e.g., as described in U.S. Patent No. 3,220,972). Complexes of chloroplatinic acid and olefins (e.g., as described in U.S. Patent Nos. 3,159,601, 3,159,662, and 3,775,452). Platinum group metals such as platinum black or palladium supported on a carrier such as alumina, silicon dioxide, or carbon. Rhodium-olefin complexes. Trichlorotriphenylphosphine rhodium (i.e., Wilkinson catalyst). Complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes).

[0035] The amount of catalyst used is called catalyst amount. Generally, the platinum group metals are preferably 0.001 to 0.1% by mass relative to the total amount of the reacting polymer. Solvents may also be used in the aforementioned polymerization reaction as needed. Hydrocarbon solvents such as toluene and xylene are preferred. Regarding the aforementioned polymerization conditions, from the viewpoint of not deactivating the catalyst and completing the polymerization in a short time, a polymerization temperature of 40 to 150°C, especially 60 to 120°C, is preferred. Although the polymerization time varies depending on the type and amount of polymer, it is preferable to complete it in approximately 0.5 to 100 hours, especially within 0.5 to 30 hours, to prevent moisture from entering the polymerization system. After the polymerization reaction is completed in this manner, if solvent was used, it is obtained by distilling it off to obtain the aforementioned polymer.

[0036] The reaction method is not particularly limited. However, it is preferable to first heat the mixture of the compound represented by formula (2), the compound represented by formula (4), and the compound represented by formula (3) as needed, then add a metal catalyst to the mixture, and then drip the compound represented by formula (1) over 0.1 to 5 hours.

[0037] The raw material compounds are preferably blended such that the total number of hydroxyl groups in the compound represented by formula (1) relative to the total number of alkenyl groups in the compounds represented by formula (2), formula (3), and formula (4), in molar ratio, is 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw system of the polymer of the present invention can be controlled by using monoallyl compounds such as o-allylphenol, or monohydrosilanes or monohydrosiloxanes such as triethylhydrosilane as molecular weight adjusters.

[0038] The polymer of the present invention is preferably a film with a thickness of 10 μm made of the polymer and a transmittance of light with a wavelength of 400 nm of 95% or more.

[0039] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) the aforementioned polymer containing a silylphenyl backbone and (B) a photoacid generator.

[0040] [(B) Photoacid generator] (B) The photoacid generating agent of component (B) is not particularly limited if it can be decomposed by light irradiation and produce acid; however, it is preferable if it produces acid by irradiation with light of wavelength 190-500 nm. (B) The photoacid generating agent is used as a curing catalyst. Examples of the aforementioned photoacid generating agents include onium salts, diazomethane derivatives, dioxime derivatives, β-ketosulfonate derivatives, dioxonate derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, amide-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc.

[0041] Examples of the aforementioned sulphur salts include sulphur salts represented by formula (B1) or sulphur salts represented by formula (B2).

[0042] In formulas (B1) and (B2), R101 to R105 are each independently a saturated hydrocarbon group with 1 to 12 carbon atoms that may have substituents, an aryl group with 6 to 12 carbon atoms that may have substituents, or an aralkyl group with 7 to 12 carbon atoms that may have substituents. A- is a non-nucleophilic relative ion.

[0043] The aforementioned saturated hydrocarbon groups can be linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Examples of aralkyl groups include benzyl and phenethyl.

[0044] Examples of substituents mentioned above include oxo groups, saturated hydrocarbon groups with 1 to 12 carbon atoms, saturated hydrocarbon oxy groups with 1 to 12 carbon atoms, aryl groups with 6 to 24 carbon atoms, aralkyl groups with 7 to 25 carbon atoms, aryloxy groups with 6 to 24 carbon atoms, and arylthio groups with 6 to 24 carbon atoms.

[0045] As R 101 to R 105, saturated hydrocarbon groups that may have substituents, such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; aryl groups that may have substituents, such as phenyl, naphthyl, biphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 3- or 4-tert-butoxyphenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, biphenylphenylthio, etc.; and aralkyl groups that may have substituents, such as benzyl, phenethyl, etc., are preferred. Among these, aryl groups that may have substituents and aralkyl groups that may have substituents are more preferred.

[0046] As the aforementioned non-nucleophilic relative ions, these include halide ions such as chloride ions and bromide ions; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; aryl sulfonate ions such as toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkane sulfonate ions such as methanesulfonate ions and butanesulfonate ions; fluoroalkane sulfonate ions such as trifluoromethanesulfonylimide ions; fluoroalkane sulfonylmethyl ions such as tri(trifluoromethanesulfonyl)methyl ions; and borate ions such as tetraphenylborate ions and tetra(pentafluorophenyl)borate ions.

[0047] As a diazomethane derivative mentioned above, a compound represented by the following formula (B3) can be cited.

[0048] In formula (B3), R111 and R112 are each independently a saturated hydrocarbon group or a halogenated saturated hydrocarbon group with 1 to 12 carbon atoms, an aryl group with 6 to 12 carbon atoms that may have substituents, or an aralkyl group with 7 to 12 carbon atoms.

[0049] Examples of the aforementioned saturated hydrocarbon groups are the same as those exemplified as saturated hydrocarbon groups represented by R 101 to R 105. Examples of the aforementioned halogenated saturated hydrocarbon groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl.

[0050] Examples of aryl groups that may have substituents include phenyl groups; alkoxyphenyl groups such as 2-, 3-, or 4-methoxyphenyl, 2-, 3-, or 4-ethoxyphenyl, and 3-, or 4-tert-butoxyphenyl; alkylphenyl groups such as 2-, 3-, or 4-methylphenyl, 2-, 3-, or 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; and halogenated aryl groups such as fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of aralkyl groups include benzyl and phenethyl groups.

[0051] As a derivative of the aforementioned dioxime, the compound represented by the following formula (B4) can be cited.

[0052] In formula (B4), R121 to R124 are each independently a saturated hydrocarbon group or a halogenated saturated hydrocarbon group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms that may have substituents. Furthermore, R123 and R124 can also bond to each other to form a ring with the carbon atoms they are bonded to. In the case of ring formation, the group formed by the bond between R123 and R124 is an alkane dimethyl group having 1 to 12 carbon atoms.

[0053] Examples of the aforementioned saturated hydrocarbon groups, halogenated saturated hydrocarbon groups, aryl groups that may have substituents, and aralkyl groups are the same as those exemplified as saturated hydrocarbon groups, halogenated saturated hydrocarbon groups, aryl groups that may have substituents, and aralkyl groups represented by R 111 and R 112. Examples of the aforementioned alkane dimethyl groups include methylene, ethyl, propane dimethyl, butane dimethyl, and hexane dimethyl.

[0054] Specifically, examples of the aforementioned onium salts include diphenyltrifluoromethanesulfonate, p-tert-butoxyphenyltrifluoromethanesulfonate, diphenyltrifluorotoluenesulfonate, p-tert-butoxyphenyltrifluoromethanesulfonate, triphenylstrontium trifluoromethanesulfonate, p-tert-butoxyphenyltrifluoromethanesulfonate, and bis(p-tert-butoxyphenyl)phenylstrontium trifluoromethanesulfonate. Tris(p-tert-butoxyphenyl) strontium trifluoromethanesulfonate, p-triphenyl strontium p-toluenesulfonate, p-diphenyl strontium p-toluenesulfonate (p-tert-butoxyphenyl)toluenesulfonate, bis(p-tert-butoxyphenyl) strontium p-tris(p-tert-butoxyphenyl) strontium p-toluenesulfonate, triphenyl strontium nonafluorobutanesulfonate, triphenyl strontium butanesulfonate, trimethyl strontium trifluoromethanesulfonate, trimethyl p-toluenesulfonate Cyclohexylmethyl(2-oxocyclohexyl) strontium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl) strontium p-toluenesulfonate, dimethylphenyl strontium trifluoromethanesulfonate, dimethylphenyl strontium p-toluenesulfonate, dicyclohexylphenyl strontium trifluoromethanesulfonate, dicyclohexylphenyl strontium p-toluenesulfonate, bis(4-tert-butylphenyl)monazine hexafluorophosphate, 4-(phenylthio)phenyldiphenylstrontium tri(pentafluoroethyl)trifluorophosphate Ester, diphenyl(4-thiophenoxyphenyl) strontium hexafluoroantimonate, [4-(4-biphenylphenylthio)phenyl]-4-biphenylphenyl strontium tri(trifluoromethanesulfonyl)methyl compound, triphenyl strontium tetra(fluorophenyl)borate, tri[4-(4-acetylatedphenyl)phenylthio] strontium tetra(fluorophenyl)borate, triphenyl strontium tetra(pentafluorophenyl)borate, tri[4-(4-acetylatedphenyl)phenylthio] strontium tetra(pentafluorophenyl)borate, etc.

[0055] Specifically, examples of the aforementioned diazonium methane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylbenzenesulfonyl)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, and bis(t... 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-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc.

[0056] Specifically, examples of the aforementioned dioxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethyldioxime, bis-o-(p-toluenesulfonyl)-α-diphenyldioxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexyldioxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedionedioxime, and bis-(p-toluenesulfonyl)-2-methyl- 3,4-Pentanedione oxime, bis-o-(n-butanesulfonyl)-α-dimethyl oxime, bis-o-(n-butanesulfonyl)-α-diphenyl oxime, bis-o-(n-butanesulfonyl)-α-dicyclohexyl oxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione oxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione Dioxime, bis-o-(methanesulfonyl)-α-dimethyldioxime, bis-o-(trifluoromethanesulfonyl)-α-dimethyldioxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethyldioxime, bis-o-(tert-butanesulfonyl)-α-dimethyldioxime, bis-o-(perfluorooctanesulfonyl)-α-dimethyldioxime, bis-o-(cyclo Hexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, etc.

[0057] Specifically, examples of the aforementioned β-keto derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0058] As examples of the aforementioned di-di ...

[0059] Specifically, examples of the aforementioned nitrobenzyl sulfonate derivatives include p-toluenesulfonic acid 2,6-dinitrobenzyl ester and p-toluenesulfonic acid 2,4-dinitrobenzyl ester.

[0060] Specifically, examples of the aforementioned sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0061] Specifically, examples of the aforementioned nitrilo-imino-sulfonate derivatives include phthalimino-trifluoromethanesulfonate, phthalimino-toluenesulfonate, 5-norcamphen-2,3-dicarboxynitrilo-trifluoromethanesulfonate, 5-norcamphen-2,3-dicarboxynitrilo-toluenesulfonate, 5-norcamphen-2,3-dicarboxynitrilo-n-butylsulfonate, and n-trifluoromethylsulfonyluoxynaphthylimino.

[0062] As examples of the aforementioned oxime sulfonate derivatives, α-(benzoyloxyimino)-4-methylphenylacetonitrile and the like can be cited.

[0063] Specifically, examples of the aforementioned iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, etc.

[0064] Furthermore, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc., can also be used appropriately.

[0065] The content of component (B) relative to 100 parts by mass of component (A) is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass. If the content of component (B) is within the aforementioned range, sufficient photocurability can be easily obtained, and the light absorption of the photoacid generator itself can effectively prevent the deterioration of curability in thick films. Furthermore, in order to obtain the transparency and lightfastness characteristic of the present invention, the amount of photoacid generator in component (B) with light absorption properties should be as low as possible without hindering photocurability. The photoacid generator in component (B) can be used alone or in combination with two or more.

[0066] [(C) Cationic polymerizable crosslinking agent] The photosensitive resin composition of the present invention may further include a cationic polymerizable crosslinking agent as component (C). Since the aforementioned cationic polymerizable crosslinking agent can undergo a cationic polymerization reaction with the epoxy group of component (A), it is not only a component that can easily form patterns, but also a component that can further improve the strength of the resin film after photocuring.

[0067] As the aforementioned crosslinking agent, compounds with a molecular weight of 100 to 15,000 are preferred, and compounds with a molecular weight of 200 to 1,000 are even more preferred. A molecular weight of 100 or higher provides sufficient photocurability, but to avoid concerns about deterioration of the heat resistance after photocuring, a molecular weight of 15,000 or lower is preferred. Furthermore, the aforementioned compound can be a resin (polymer), in which case the molecular weight is the weight average molecular weight (Mw).

[0068] As the aforementioned cationic polymerizable crosslinking agent, compounds having functional groups selected from epoxy, propylene oxide, and vinyl ether groups are preferred. Such compounds may be used alone or in combination of two or more.

[0069] The content of component (C) relative to 100 parts by mass of component (A) is 0 to 100 parts by mass. However, when it is present, 0.5 to 100 parts by mass is preferred, 0.5 to 60 parts by mass is more preferred, and 1 to 50 parts by mass is even more preferred. If the content of component (C) is 0.5 parts by mass or more, sufficient curing properties can be obtained upon light irradiation. If it is less than 100 parts by mass, the proportion of component (A) in the photosensitive resin composition will not decrease, thus allowing the cured material to fully exhibit the effects of the present invention. Component (C) can be used alone or in combination of two or more.

[0070] [(D) solvent] To improve the coatability of the photosensitive resin composition of the present invention, a solvent may also be included as component (D). As the solvent (D), it is not particularly limited to any solvent that can dissolve the aforementioned components (A) to (C), as well as component (E) or other various additives described below.

[0071] As solvent (D), organic solvents are preferred. Specific examples include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as 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, and γ-butyrolactone. One of these solvents may be used alone, or two or more may be used in combination.

[0072] As a solvent for (D), ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof are preferred, especially those with excellent solubility for photoacid generators.

[0073] From the perspective of the compatibility and viscosity of the photosensitive resin composition, the content of component (D) is better at 50 to 2,000 parts by weight than 100 parts by weight of component (A), even better at 50 to 1,000 parts by weight, and even better at 50 to 100 parts by weight.

[0074] (E) Antioxidants The photosensitive resin composition of the present invention may also include antioxidants as additives. By including antioxidants, heat resistance can be improved. Examples of such antioxidants include hindered phenolic compounds and hindered amine compounds.

[0075] As for the aforementioned hindered phenolic compounds, there is no particular limitation, however, the following are preferred. 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 (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX). 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4'-butylenebis(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'-vinylbis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adekastab AO-30), tetra[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: Adekastab) AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-Triazine (trade name: IRGANOX 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamoylamine) (trade name: IRGANOX 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 259), 2,2-thio-divinylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5,5]undecane (trade name: Sumilizer) GA-80), tri-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax mixture (50:50) (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-butyldibenzo[d,f][1,3,2]dioxophosphoric acid heptane (trade name: Sumilizer GP), etc. ,

[0076] The aforementioned hindered amine compounds are not particularly limited, however, the following are preferred. Examples include p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade names: 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), and 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac). CD), p,p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacryloxy-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-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-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)vinyldiamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-Pentamethyl-4-piperidinyl (trade name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (trade name: TINUVIN) 765), tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), a mixed ester of 1,2,3,4-butanetetracarboxylate with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tetranol (trade name: LA-62), a mixed ester of 1,2,3,4-butanetetracarboxylate with 2,2,6,6-tetramethyl-4-piperidinol and 1-tetranol (trade name: LA-67), 1,2,3,4-butane Mixed esters of tetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-63P), mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: LA-68LD), and (2,2,6,6-tetramethylene-4-piperidinyl)-2-propylcarboxylate (trade name: Adekastab) Examples include LA-82 and (1,2,2,6,6-pentamethyl-4-piperidinyl)-2-enylpropylcarboxylate (trade name: Adekastab LA-87).

[0077] (E) The content of component (E) is not particularly limited without impairing the effects of the present invention; however, when it is included, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention. (E) The antioxidant of component (E) may be used alone or in combination with two or more.

[0078] [Other additives] In addition to the aforementioned components, the photosensitive resin composition of the present invention may also contain other additives. Examples of additives include, for instance, commonly used surfactants for improving coatability.

[0079] As for the aforementioned surfactants, nonionic surfactants are preferred. For example, fluorinated surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorinated organosiloxane compounds, can be used. These are commercially available products, such as Fluorad (registered trademark) "FC-430" (manufactured by 3M Corporation), Surflon (registered trademark) "S-141" and "S-145" (manufactured by AGC SEIMI CHEMICAL), UNIDYNE (registered trademark) "DS-401", "DS-4031" and "DS-451" (manufactured by Daikin Industries, Ltd.), Megafac (registered trademark) "F-8151" (manufactured by DIC Corporation), and "X-70-093" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). Among these, Fluorad "FC-430" and "X-70-093" are preferred. The content of the aforementioned surfactants is not particularly limited without impairing the effects of the present invention; however, when present, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

[0080] Furthermore, silane coupling agents can be used as additives. By including silane coupling agents, the adhesion of the photosensitive resin composition to the substrate can be further improved. Examples of silane coupling agents include epoxy silane coupling agents and aromatic amino silane coupling agents. These can be used alone or in combination of two or more. The content of the aforementioned silane coupling agent is not particularly limited without impairing the effects of the present invention; however, when included, it is preferably 0.01 to 5% by mass in the photosensitive resin composition of the present invention.

[0081] The method for preparing the photosensitive resin composition of the present invention is not particularly limited; however, for example, the aforementioned components may be stirred and mixed, and then filtered as needed using a filter or similar means for removing solid components.

[0082] [Graphic Formation Method] The pattern forming method of the present invention uses the aforementioned photosensitive resin composition, and comprises: (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 previously exposed photosensitive resin film using a developing solution. This method can obtain fine patterns.

[0083] Step (i) is the 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 boards, and ceramic circuit boards.

[0084] The photosensitive resin film can be formed by known methods. For example, it can be formed by coating the aforementioned photosensitive resin composition onto a substrate using methods such as dip coating, spin coating, or roll coating. The coating amount can be appropriately selected according to the purpose, but it is preferable to make the film thickness an amount of 0.1 to 100 μm.

[0085] Here, in order to ensure the efficient conduction of the photocuring reaction, preheating can be performed as needed to allow the solvent to evaporate beforehand. Preheating can be carried out, for example, at 40~160°C for 1 minute to 1 hour.

[0086] Next, as step (ii), the aforementioned photosensitive resin film is exposed. Preferably, the exposure is performed with light of a wavelength of 240-500 nm. Examples of light of the aforementioned wavelength of 240-500 nm include light of various wavelengths produced by radiation-generating devices, such as ultraviolet light (gamma rays, i rays, etc.) and far-ultraviolet light (248 nm). The exposure amount is preferably 10-5,000 mJ / cm².

[0087] Exposure can also be performed through a photomask. The aforementioned photomask can be, for example, one with the desired pattern cut out. In addition, the material of the photomask is preferably one that blocks the aforementioned wavelength of light in the range of 240~500nm, such as chromium, but it is not limited to this.

[0088] In addition, to further improve the image sensitivity, post-exposure heat treatment (PEB) can be performed. PEB, for example, can be set at 40~160°C for 5~30 minutes.

[0089] Step (iii) involves developing the photosensitive resin film using a developing solution after exposure or PEB. As the developing solution, an organic solvent-based developing solution is preferred, such as isopropyl alcohol, propylene glycol monomethyl ether, or propylene glycol monomethyl ether acetate. By using the aforementioned organic solvent-based developing solution, a negative pattern can be obtained after dissolving and removing the non-exposed areas. The developing process can be performed using conventional methods, such as immersing the patterned substrate in the developing solution. Afterwards, washing, rinsing, and drying are performed as needed to obtain a film with the desired pattern.

[0090] Furthermore, the method for forming the pattern is as described above. However, in cases where it is not necessary to form a pattern, such as when it is only necessary to form a uniform film, in step (ii) of the aforementioned pattern forming method, the film can be formed by exposing the film to light of an appropriate wavelength without separating it from the aforementioned photomask.

[0091] In addition, as needed, (iv) the patterned film can be further heated in an oven or on a heating plate at 80~300°C for 10 minutes to 10 hours to increase the crosslinking density and remove residual volatile components (post-curing).

[0092] [Optical Semiconductor Components] By using the aforementioned photosensitive resin composition and forming fine patterns using the aforementioned method, optical semiconductor devices can be manufactured. Furthermore, the film obtained from the aforementioned photosensitive resin composition exhibits excellent transparency, lightfastness, and heat resistance, and the optical semiconductor device possessing this film is suitable for use in optical devices such as light-emitting elements like light-emitting diodes, light-receiving elements like optical sensors, light waveguides, and light transmission devices. The transmittance of the aforementioned film for light at a wavelength of 400 nm is preferably 92% or higher, more preferably 96% or higher, and particularly preferably 98% or higher. [Example]

[0093] The present invention is described below with reference to examples and comparative examples; however, the present invention is not limited to the examples described below. In addition, in the examples described below, Mw was determined by using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column, with an analytical conditions of 0.6 mL / min flow rate, THF dissolution solvent, and column temperature of 40°C, by using monodisperse polystyrene as a standard GPC.

[0094] [1] Synthesis and evaluation of polymers The compounds used in the synthesis of polymers are shown below.

[0095]

[0096]

[0097]

[0098]

[0099] [Example 1-1] Synthesis of Polymer 1 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 53.0 g (0.20 mol) of the compound represented by formula (S-2), 48.1 g (0.40 mol) of the compound represented by formula (S-3a), and 85.7 g (0.40 mol) of the compound represented by formula (S-4a) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 1. The Mw of polymer 1 is 16,000. Furthermore, polymer 1 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0100] [Examples 1-2] Synthesis of Polymer 2 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 159g (0.60 mol) of the compound represented by formula (S-2), 24.0g (0.20 mol) of the compound represented by formula (S-3a), and 42.9g (0.20 mol) of the compound represented by formula (S-4a) were added, followed by the addition of 700g of toluene, and the mixture was heated to 70°C. Then, 1.0g of a chloroplatinic acid-toluene solution (platinum concentration 0.5% by mass) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 2. The Mw of polymer 2 is 15,000. Furthermore, polymer 2 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0101] [Examples 1-3] Synthesis of Polymer 3 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 92.8 g (0.35 mol) of the compound represented by formula (S-2), 56.8 g (0.35 mol) of the compound represented by formula (S-3b), and 64.3 g (0.30 mol) of the compound represented by formula (S-4a) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 3. The Mw of polymer 3 is 12,000. Furthermore, polymer 3 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0102] [Examples 1-4] Synthesis of Polymer 4 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 106g (0.40 mol) of the compound represented by formula (S-2), 32.5g (0.20 mol) of the compound represented by formula (S-3b), and 85.7g (0.40 mol) of the compound represented by formula (S-4a) were added, followed by the addition of 700g of toluene, and the mixture was heated to 70°C. Then, 1.0g of a chloroplatinic acid-toluene solution (platinum concentration 0.5% by mass) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 4. The Mw of polymer 4 is 13,000. Furthermore, polymer 4 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0103] [Examples 1-5] Synthesis of Polymer 5 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 53.0 g (0.20 mol) of the compound represented by formula (S-2), 24.0 g (0.20 mol) of the compound represented by formula (S-3a), and 103 g (0.60 mol) of the compound represented by formula (S-4b) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 5. The Mw of polymer 5 is 9,000. Furthermore, polymer 5 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0104] [Examples 1-6] Synthesis of Polymer 6 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 79.5 g (0.30 mol) of the compound represented by formula (S-2), 32.5 g (0.20 mol) of the compound represented by formula (S-3b), and 86.1 g (0.50 mol) of the compound represented by formula (S-4b) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 6. The Mw of polymer 6 is 8,000. Furthermore, polymer 6 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1), repeating units represented by formula (A2), and repeating units represented by formula (A3).

[0105] [Examples 1-7] Synthesis of Polymer 7 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 106g (0.40 moles) of the compound represented by formula (S-2) and 129g (0.60 moles) of the compound represented by formula (S-4a) were added, followed by 700g of toluene, and the mixture was heated to 70°C. Then, 1.0g of a chloroplatinic toluene solution (platinum concentration 0.5% by mass) was added, and 192g (0.99 moles) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mole ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain polymer 7. The Mw of polymer 7 is 11,000. Furthermore, polymer 7 was confirmed by 1H-NMR (manufactured by Bruker Corporation) to be a polymer containing repeating units represented by formula (A1) and repeating units represented by formula (A3).

[0106] [Comparative Example 1-1] Comparison of the synthesis of polymer 1 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 53.0 g (0.20 mol) of the compound represented by formula (S-2), 48.1 g (0.40 mol) of the compound represented by formula (S-3a), and 56.5 g (0.40 mol) of the compound represented by formula (S-5a) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic acid-toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain comparative polymer 1. The Mw of comparative polymer 1 is 10,000.

[0107] [Comparative Examples 1-2] Comparison of the synthesis of polymer 2 In a 10L flask equipped with a stirrer, thermometer, nitrogen substitution apparatus, and reflux cooler, 92.8 g (0.35 mol) of the compound represented by formula (S-2), 56.8 g (0.35 mol) of the compound represented by formula (S-3b), and 59.8 g (0.30 mol) of the compound represented by formula (S-5b) were added, followed by the addition of 700 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of a chloroplatinic acid-toluene solution (platinum concentration 0.5% by mass) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total hydrosilyl groups:total alkenyl groups = 0.99:1 (mol ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and matured for 8 hours. The toluene was then removed from the reaction solution by vacuum distillation to obtain comparative polymer 2. The Mw of comparative polymer 2 is 12,000.

[0108] [Light transmittance test 1] Polymer solutions were prepared by dissolving polymers 1-7 and comparative polymers 1 and 2 in cyclopentanone to a concentration of 50% by mass. Each polymer solution was coated onto a glass substrate and heated at 60°C for 30 minutes, followed by heating at 190°C for 2 hours under nitrogen atmosphere to form a film (10 μm thick). The transmittance of light at a wavelength of 400 nm was measured for each obtained film. The results are shown in Table 1. Furthermore, the film thickness was measured using an optical interferometric film thickness measuring device manufactured by SCREEN, based on the film thickness of films previously formed on silicon wafers under the same conditions.

[0109]

[0110] [Light transmittance test 2] In an oven at 50°C, a sample consisting of a film on a glass wafer obtained by the aforementioned method was continuously irradiated with a 400 nm, 1 W laser. The rate of change in light transmittance was investigated when the initial stage (before laser irradiation) was set to 100%, after 100 hours, and after 1,000 hours. The results are shown in Table 2.

[0111]

[0112] [Hardening Temperature Measurement Experiment 1] For polymers 1-7, and comparative polymers 1 and 2, 3 parts by mass of CPI-210S (manufactured by San-Apro) were added as photoacid generators, and cyclopentanone was added to achieve a solid concentration of 50% by mass until homogeneous. 2 g of each solution was placed in an aluminum petri dish and heated at 100°C for 15 minutes to dry. The remaining solid was exposed to 3,000 mJ of light at 365 nm, and differential scanning calorimetry (DSC) was performed. The curing temperature was evaluated using the exothermic peak. The results are shown in Table 3. Furthermore, the DSC was performed using a TA Instruments Q2000, with the temperature increased from 0°C to 200°C at a rate of 10°C per minute to determine the curing temperature.

[0113]

[0114] [2] Modulation and evaluation of photosensitive resin composition [Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-8] The solvents for polymers 1-7, comparative polymers 1 and 2 as component (A), photoacid generators B-1 and B-2 as component (B), crosslinking agents C-1, C-2 and C-3 as component (C), and cyclopentanone (CP) as component (D) were mixed in such a manner as shown in Tables 4 and 5 below, and stirred to dissolve. The mixture was then precisely filtered using a 0.2 μm filter made of Teflon (registered trademark) to prepare the photosensitive resin composition.

[0115]

[0116]

[0117] In Tables 4 and 5, photoacid generators B-1 and B-2, and crosslinking agents C-1, C-2 and C-3 are as follows. • Photoacid generators B-1 and B-2: (In the formula, Rf represents a perfluoroalkyl group. b represents 0~6.)

[0118] Crosslinking agents C-1, C-2, C-3:

[0119] [Graphic Formation Evaluation] On an 8-inch silicon wafer pretreated with hexamethyldisilazane, a spin coater was used to coat various photosensitive resin compositions to a thickness of 10 μm. To remove the solvent from the compositions, the wafer was placed on a hot plate and heated at 110°C for 3 minutes to dry it. The resulting photosensitive resin film was then used as a mask to form line and gap patterns and contact hole patterns, and exposed using a contact alignment exposure apparatus at 365 nm. After exposure, the wafer was subjected to PEB at 120°C for 3 minutes on a hot plate, cooled, and then spray-developed with propylene glycol monomethyl ether acetate (PGMEA) for 300 seconds to form the pattern.

[0120] The photosensitive resin film on the wafer with the pattern formed by the aforementioned method was post-cured for 2 hours in an oven at 190°C while being purged with nitrogen. Afterwards, the cross-sections of the formed contact hole patterns of 50μm, 30μm, 20μm, 10μm, and 5μm were observed using a scanning electron microscope (SEM), and the smallest hole pattern extending to the bottom of the film was taken as the limiting resolution. Furthermore, the perpendicularity of the 50μm contact hole pattern was evaluated from the obtained cross-sectional photographs, with perpendicular patterns designated as ◎, slightly inverted conical shapes as ○, inverted conical shapes as △, and poor openings as ×. The results are shown in Tables 6 and 7.

[0121]

[0122]

[0123] [Light transmittance test 1] On an 8-inch glass wafer, a spin coater was used to coat various photosensitive resin compositions to a thickness of 20 μm. To remove the solvent from the compositions, the glass wafer was placed on a hot plate and heated at 110°C for 3 minutes to dry it. The entire composition coated on the glass wafer was then immersed in PGMEA without a mask, using a SUSS MicroTec MA8 mask aligner and a high-pressure mercury lamp (wavelength 360 nm) as the light source. The remaining film was then further heated in an oven at 190°C for 2 hours to obtain the final film. The transmittance of this film at a wavelength of 400 nm was measured using a spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation). The results are shown in Tables 8 and 9.

[0124]

[0125]

[0126] [Light transmittance test 2] In an oven at 50°C, a sample consisting of a film on a glass wafer obtained by the aforementioned method was continuously irradiated with a laser of 400 nm and 1 W. The rate of change of light transmittance was investigated when the initial stage (before laser irradiation) was set to 100%, after 100 hours, and after 1,000 hours. The results are shown in Tables 10 and 11.

[0127]

[0128]

[0129] [Hardening Temperature Measurement Test] Two g of each photosensitive resin component was placed in an aluminum petri dish and heated at 100°C for 15 minutes, then dried. The remaining solid was exposed to 3,000 mJ of light at 365 nm, and differential scanning calorimetry (DSC) was performed. The curing temperature was evaluated using the exothermic peak. The DSC was performed using a TA Instruments Q2000, increasing the temperature from 0°C to 200°C at a rate of 10°C per minute. The results are shown in Figures 12 and 13.

[0130]

[0131]

[0132] Based on the above results, the main chain of the present invention comprises a silylphenyl backbone, an isocyanuric acid backbone, and a hydroxyl-substituted alkyl ether backbone, and is a polymer containing epoxy groups in the side chains, exhibiting excellent low-temperature curing properties. Furthermore, the film obtained from the polymer of the present invention is a film with high transparency and high lightfastness. In addition, the photosensitive resin composition containing the polymer of the present invention can be microprocessed and can provide a film with excellent low-temperature curing properties, high transparency, and high lightfastness.

Claims

1. A polymer comprising a silylphenyl backbone, a cyanuric acid backbone, and a hydroxyl-substituted alkyl ether backbone in its main chain, and comprising epoxy groups in its side chains, wherein the polymer comprises repeating units represented by formula (A1), formula (A2), and formula (A3): (where a, b, and c are positive numbers satisfying 0 < a < 1, 0 ≦ b < 1, 0 < c < 1, and a + b + c = 1; X1 is a divalent base represented by formula (X1); X2 is a divalent base represented by formula (X2); and X3 is a divalent base represented by formula (X3)) (In the formula, R11 and R12 are each independently a hydrogen atom or a methyl group; R13 is an alkyl group with 1 to 8 carbon atoms, and ester or ether bonds may exist between their carbon-carbon bonds; n1 and n2 are each independently an integer from 0 to 7; the dashed lines represent bonded bonds.) (In the formula, R21 and R22 are each independently a hydrogen atom or a saturated alkyl group with 1 to 20 carbon atoms that may contain heteroatoms; m is an integer from 0 to 10; the dashed lines represent bonded bonds.) (In the formula, R31 and R32 are each independently a hydrogen atom or a methyl group; R33 is a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When R33 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent; R34 is a hydroxyl group or a saturated hydrocarbon group with 1 to 20 carbon atoms that may contain heteroatoms. When R34 is a saturated hydrocarbon group, it may also contain a primary or secondary alcoholic hydroxyl group as a substituent; when R33 is a hydrogen atom and R34 is a saturated hydrocarbon group, R34 contains at least one primary or secondary alcoholic hydroxyl group as a substituent; when R33 and R34 are both saturated hydrocarbon groups, one or both contain at least one primary or secondary alcoholic hydroxyl group as a substituent; p1 and p2 are each independently an integer from 1 to 7; q1 and q2 are each independently an integer from 1 to 7; the dashed lines represent bonded bonds).

2. The polymer as described in claim 1, wherein, The number of carbons contained in the divalent radical represented by formula (X3) is 9 to 20.

3. The polymer as described in claim 1 or 2, wherein, a, b, and c are positive numbers that satisfy 0 < a < 1, 0 < b < 1, 0 < c < 1, and a + b + c = 1.

4. The polymer as described in claim 1 or 2, wherein, R34 is a straight-chain alkyl group with a terminal hydroxyl group.

5. The polymer as described in claim 1 or 2, wherein, R31 and R32 are hydrogen atoms.

6. The polymer as described in claim 1 or 2, wherein, p1 and p2 are both 1.

7. The polymer as described in claim 1 or 2, wherein, q1 and q2 are both 1.

8. The polymer as described in claim 1 or 2, wherein, The 10μm thick film composed of the aforementioned polymer has a light transmittance of over 95% at a wavelength of 400nm.

9. A photosensitive resin composition comprising the polymer as described in any one of claims 1 to 8 and (B) a photoacid generator.

10. The photosensitive resin composition as described in claim 9, wherein, It further includes (C) a cationic polymerizable crosslinking agent.

11. A pattern forming method comprising: (i) forming a photosensitive resin film on a substrate using a photosensitive resin composition as described in claim 9 or 10; (ii) exposing the aforementioned photosensitive resin film; and (iii) developing the exposed photosensitive resin film using a developer.

12. A method for manufacturing a photosensitive resin film of a photonic semiconductor device, comprising the pattern forming method as described in claim 11.

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