Silphenylene skeleton-containing polymer, photosensitive resin composition, pattern forming method, and method for manufacturing optical semiconductor device

Abstract

To provide a polymer which can be cured at a low temperature and affords a film having high transparency and high light resistance.SOLUTION: There is provided, a polymer containing a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxyl group-substituted alkyl ether skeleton in a main chain and an epoxy group in a side chain.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a silphenylene skeleton-containing polymer, a photosensitive resin composition, a pattern forming method, and a method for producing an optical semiconductor element. Regarding. [Background technology]

[0002] Transparent epoxy resins have traditionally been used as sealing and protective materials and adhesives in various optical devices, such as light-emitting diodes (LEDs), CMOS image sensors, etc. In recent years, resist materials using epoxy resins are often used, as many optical devices require microfabrication.

[0003] In recent years, optical devices such as LEDs have become increasingly powerful, and they are required to be microfabricated and have higher transparency and light resistance than ever before in order to suppress gas generation, discoloration, etc. As a material that can be microfabricated and has particularly high transparency and light resistance, there is, for example, a photosensitive material that uses an epoxy-modified silicone resin into which isocyanuric acid and a norbornene skeleton have been introduced (Patent Document 1).

[0004] Recently, in addition to transparency and light resistance, further improvements in properties are required for such photosensitive materials, and in particular, low-temperature curing is required. However, the above-mentioned epoxy-modified silicone resin is not a material that can be cured at a low temperature of about 130°C. Therefore, a photosensitive material using a resin that has not only epoxy groups but also other highly reactive functional groups has been desired. Introducing other highly reactive functional groups into the epoxy resin is expected to not only enable low-temperature curing, but also contribute to improving processability. Therefore, it becomes a high-added-value material that can be finely processed and cured at low temperatures. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-90649 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer that is capable of forming a fine pattern over a wide wavelength range while being cured at a low temperature and capable of providing a coating having 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 problem]

[0007] As a result of extensive investigations to achieve the above-mentioned object, the present inventors have found that a polymer which contains a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxy group-substituted alkyl ether skeleton in its main chain and an epoxy group in its side chain can be cured at low temperatures to give a coating which has high transparency and high light resistance, and that a photosensitive resin composition which contains the polymer of the present invention and a photoacid generator is capable of forming a fine pattern over a wide wavelength, yet can be cured at low temperatures to give a coating which has high transparency and high light resistance, and have completed the present invention.

[0008] That is, the present invention provides the following silphenylene skeleton-containing polymer, photosensitive resin composition, pattern forming method, and method for producing an optical semiconductor element. 1. A polymer containing a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxyl-substituted alkyl ether skeleton in the main chain and containing an epoxy group in the side chain. 2. The polymer of 1, wherein the hydroxy group-substituted alkyl ether skeleton has 9 to 20 carbon atoms. 3. A 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). [ka] (wherein a, b, and c are positive numbers satisfying 0 < a < 1, 0 ≤ b < 1, 0 < c < 1, and a + b + c = 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). X 3 is a divalent group represented by the following formula (X3).)

Chemical formula

Chemical formula

Chemical formula

[0009] The polymer of the present invention can be cured at low temperatures, particularly at low temperatures of 130°C or lower, and provides a film having high transparency and high light resistance. The polymer of the present invention can be easily synthesized. Further, by using the photosensitive resin composition containing the polymer of the present invention, a fine pattern can be formed using light of a wide range of wavelengths. Furthermore, the film obtained from the photosensitive resin composition of the present invention is excellent in transparency and light resistance, can be cured at a low temperature of 130°C or lower, and can be suitably used for protecting and sealing optoelectronic devices. [Embodiments for Carrying Out the Invention]

[0010] [Polymer Containing a Silphenylene Skeleton] The polymer of the present invention is a polymer containing a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxy group-substituted alkyl ether skeleton in the main chain and an epoxy group in the side chain. The number of carbon atoms of the hydroxy group-substituted alkyl ether skeleton is preferably 9 to 20. The polymer may further contain a norbornene skeleton in the main chain.

[0011] As such a polymer, those 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) are preferable. [Chemical Formula]

[0012] 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.

[0013] In formula (A1), X 1 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. [Chemical Formula] (The dashed lines represent bonds.)

[0014] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group.

[0015] In formula (X1), R 13 R is a hydrocarbylene group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be present between the carbon-carbon bonds. 13 The hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include alkanediyl groups such as a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group. 13 is preferably a methylene group or an ethylene group, more preferably a methylene group. An ester bond or an ether bond may be present between the carbon-carbon bonds of the hydrocarbylene group.

[0016] In formula (X1), n 1 and n 2 are each independently an integer of 0 to 7.

[0017] In formula (A2), X 2 is a divalent group represented by the following formula (X2): The divalent group represented by the following formula (X2) is a group having a norbornene skeleton. [ka] (The dashed lines represent bonds.)

[0018] In formula (X2), R 21 and R 22are each independently a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, or an n-decyl group; and cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group. The saturated hydrocarbyl group may contain a heteroatom. Specifically, some or all of the hydrogen atoms of the saturated hydrocarbyl group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and a carbonyl group, an ether bond, a thioether bond, etc. may be present between the carbon-carbon atoms.

[0019] In formula (X2), m is an integer of 0 to 10, with 0 being preferred.

[0020] In formula (A3), X 3 is a divalent group represented by the following formula (X3): The divalent group represented by the following formula (X3) is a group having a hydroxy group-substituted alkyl ether skeleton. [ka] (The dashed lines represent bonds.)

[0021] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group, with a hydrogen atom being preferred.

[0022] In formula (X3), R 33 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom, R 33When R is a saturated hydrocarbyl group, it may contain a primary or secondary alcoholic hydroxy group as a substituent. 34 is a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a hydroxy group or a heteroatom, R 34 When R is a saturated hydrocarbyl group, it may contain a primary or secondary alcoholic hydroxy group as a substituent. 33 and R 34 The saturated hydrocarbyl group represented by the formula (X2) may be linear, branched, or cyclic. 21 and R 22 Examples of the saturated hydrocarbyl group include the same as those exemplified as the saturated hydrocarbyl group represented by the formula: In addition, the saturated hydrocarbyl group may contain a heteroatom, and specifically, a part or all of the hydrogen atoms of the saturated hydrocarbyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a carbonyl group, an ether bond, a thioether bond, or the like may be present between the carbon atoms.

[0023] R 33 is a hydrogen atom and R 34 When R is a saturated hydrocarbyl group, 34 R contains at least one primary or secondary alcoholic hydroxy group as a substituent. 33 and R 34 When R are both saturated hydrocarbyl groups, one or both of them contain at least one primary or secondary alcoholic hydroxy group as a substituent. 33 and R 34 When contains an alcoholic hydroxy group, R 33 and R 34 As the alkyl group, a straight-chain alkyl group containing a primary alcoholic hydroxy group at the terminal is preferred.

[0024] In formula (X3), p 1 and p 2 are each independently an integer of 1 to 7, preferably 1. 1 and q 2Each is independently an integer from 1 to 7, with 1 being preferred. The number of carbon atoms contained in the divalent group represented by formula (X3) is preferably from 9 to 20.

[0025] The polymer of the present invention preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. If Mw is within the above range, the polymer can be obtained as a solid, and film-forming properties can also be ensured. In the present invention, Mw is a polystyrene-equivalent measurement value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0026] The polymer of the present invention may be one in which the repeating unit represented by formula (A1), the repeating unit represented by formula (A2), and the repeating unit represented by formula (A3) are randomly bonded or alternately bonded, or may contain a plurality of blocks of each unit.

[0027] 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, but 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, and even more preferably 0.15 < a < 0.65, 0.15 < b < 0.65, 0.15 < c < 0.65.

[0028] [Method for Producing Polymer Containing Silphenylene Skeleton] The 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. [Chemical formula]

[0029] [Chemical formula] (In the formula, R 11 ~R 13 , n 1 and n 2 is the same as above.)

[0030] [ka] (In the formula, R 21 , R 22 and m are the same as above.)

[0031] [ka] (In the formula, R 31 ~R 34 , p 1 , p 2 , q 1 and q 2 is the same as above.)

[0032] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinic acid salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, and particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (for example, those described in U.S. Pat. No. 3,220,972) ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0033] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 mass% as platinum group metal relative to the total amount of the reaction polymer. In the polymerization reaction, a solvent may be used as necessary. For example, a hydrocarbon solvent such as toluene or xylene is preferable as the solvent. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is, for example, 40 to 150°C, particularly 60 to 120°C. The polymerization time depends on the type and amount of the polymer, but is preferably completed within about 0.5 to 100 hours, particularly 0.5 to 30 hours, in order to prevent moisture from entering the polymerization system. After the polymerization reaction is completed in this manner, if a solvent is used, it can be distilled off to obtain the polymer.

[0034] The reaction method is not particularly limited, but it is preferable to first mix and heat the compound represented by formula (2), the compound represented by formula (4), and, if necessary, the compound represented by formula (3), and then add a metal catalyst to the mixed solution, and then dropwise add the compound represented by formula (1) over a period of 0.1 to 5 hours.

[0035] The raw material compounds are preferably blended such that the molar ratio of the hydrosilyl group in the compound represented by formula (1) to the total of the alkenyl groups in the compound represented by formula (2), the compound represented by formula (3) and the compound represented by formula (4) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of the 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 regulator.

[0036] The polymer of the present invention is preferably one in which a film of the polymer having a thickness of 10 μm has a transmittance of 95% or more for light having a wavelength of 400 nm.

[0037] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) the above-mentioned silphenylene skeleton-containing polymer and (B) a photoacid generator.

[0038] [(B) Photoacid generator] The photoacid generator (B) is not particularly limited as long as it is decomposed by light irradiation and generates an acid, but it is preferable that it generates an acid by irradiation with light having a wavelength of 190 to 500 nm. (B) Photoacid generator 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, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0039] The onium salt includes a sulfonium salt represented by the following formula (B1) or an iodonium salt represented by the following formula (B2). [ka]

[0040] In formulas (B1) and (B2), R 101 ~R 105 are each independently a saturated hydrocarbyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0041] The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups. Examples of the aryl group include phenyl, naphthyl, and biphenylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

[0042] Examples of the substituent include an oxo group, a saturated hydrocarbyl group having 1 to 12 carbon atoms, a saturated hydrocarbyloxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms.

[0043] R 101 ~R 105 Preferred examples of the aryl group include saturated hydrocarbyl groups 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, or a 2-oxocyclohexyl group; aryl groups which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, a 3- or 4-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, a 2-, 3-, or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and aralkyl groups which may have a substituent such as a benzyl group or a phenethyl group. Of these, aryl groups which may have a substituent and aralkyl groups which may have a substituent are more preferred.

[0044] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; and borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion.

[0045] The diazomethane derivative includes a compound represented by the following formula (B3). [ka]

[0046] In formula (B3), R 111 and R 112 each independently represents a saturated hydrocarbyl group or a halogenated saturated hydrocarbyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0047] The saturated hydrocarbyl group is R 101 ~R 105 Examples of the halogenated saturated hydrocarbyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like.

[0048] Examples of the aryl group which may have a substituent include a phenyl group, an alkoxyphenyl group such as a 2-, 3- or 4-methoxyphenyl group, a 2-, 3- or 4-ethoxyphenyl group, or a 3- or 4-tert-butoxyphenyl group, an alkylphenyl group such as a 2-, 3- or 4-methylphenyl group, a 2-, 3- or 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group, and an aryl halide group such as a fluorophenyl group, a chlorophenyl group, or a 1,2,3,4,5-pentafluorophenyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0049] The glyoxime derivative includes a compound represented by the following formula (B4). [ka]

[0050] In formula (B4), R 121 ~R 124 are each independently a saturated hydrocarbyl group or a halogenated saturated hydrocarbyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. 123 and R 124 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and when they form a ring, R 123 and R 124 The group formed by bonding is an alkanediyl group having 1 to 12 carbon atoms.

[0051] The saturated hydrocarbyl group, the halogenated saturated hydrocarbyl group, the aryl group which may have a substituent, and the aralkyl group which may have a substituent are each represented by R 111 and R 112Examples of the alkanediyl group include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a hexanediyl group, and the like.

[0052] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, p-Toluenesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenyl butanesulfonate Sulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate Cyclohexylphenylsulfonium, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, 4-(phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate,Examples of the borate include tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0053] 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-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0054] Specific examples of the glyoxime derivatives 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-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis- Examples of the dimethylglyoxime include 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)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0055] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0056] Specific examples of the disulfone derivative include diphenyl disulfone and dicyclohexyl disulfone.

[0057] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0058] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0059] Specific examples of the imide-yl sulfonate derivative include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0060] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile.

[0061] Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and the like.

[0062] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0063] The content of the (B) component is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the (A) component. If the content of the (B) component is within the above range, sufficient photocurability is easily obtained, and deterioration of the curability in a thick film due to light absorption by the photoacid generator itself can be effectively prevented. In order to obtain the transparency and light resistance that are the characteristics of the present invention, the blending amount of the photoacid generator (B) having light absorption properties is preferably small within a range that does not inhibit photocurability. The photoacid generator (B) may be used alone or in combination of two or more kinds.

[0064] [(C) Cationic polymerizable crosslinking agent] The photosensitive resin composition of the present invention may further contain a cationic polymerizable crosslinking agent as component (C), which is capable of undergoing a cationic polymerization reaction with the epoxy groups of component (A) and is a component that facilitates the formation of a pattern and further increases the strength of the resin film after photocuring.

[0065] 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. If the molecular weight is 100 or more, sufficient photocurability can be obtained, and if it is 15,000 or less, it is preferable because there is no risk of deterioration of the heat resistance of the composition after photocuring. The compound may be a resin (polymer), and in that case, the molecular weight is the weight average molecular weight (Mw).

[0066] The cationic polymerizable crosslinking agent is preferably a compound having a functional group selected from an epoxy group, an oxetane group, and a vinyl ether group. These compounds may be used alone or in combination of two or more.

[0067] The content of the (C) component is 0 to 100 parts by mass relative to 100 parts by mass of the (A) component, but when contained, it is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 60 parts by mass, and even more preferably 1 to 50 parts by mass. If the content of the (C) component is 0.5 parts by mass or more, sufficient curability is obtained upon light irradiation, and if it is 100 parts by mass or less, the proportion of the (A) component in the photosensitive resin composition does not decrease, so that the cured product can fully exhibit the effects of the present invention. The (C) component can be used alone or in combination of two or more types.

[0068] [(D) Solvent] The photosensitive resin composition of the present invention may contain a solvent as component (D) in order to improve its coatability. The solvent (D) is not particularly limited as long as it can dissolve the above-mentioned components (A) to (C), the below-mentioned component (E), and various other additives.

[0069] (D) The solvent is preferably an organic solvent, and specific examples thereof include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; 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. These may be used alone or in combination of two or more.

[0070] As the (D) solvent, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof, which have particularly excellent solubility for the photoacid generator, are preferred.

[0071] From the viewpoints of compatibility and viscosity of the photosensitive resin composition, the content of the component (D) is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and even more preferably 50 to 100 parts by mass, per 100 parts by mass of the component (A).

[0072] [(E) Antioxidants] The photosensitive resin composition of the present invention may contain an antioxidant as an additive. By containing an antioxidant, the heat resistance can be improved. Examples of the antioxidant include hindered phenol compounds and hindered amine compounds.

[0073] The hindered phenol compound is not particularly limited, but the following are preferred: 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 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl- ... 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'-butylidenebis(3-methyl-6-tert-butylphenol) (Trade name: Adekastab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Trade name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name: Seenox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L), 2,2'-ethylenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-Tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adeka STAB AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]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'-hexamethylenebis(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-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid 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-butyldibenz[d,f][1,3,2]dioxaphosphepine (trade name: Sumilizer GP), etc.

[0074] The hindered amine compound is not particularly limited, but the following compounds are preferred. 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-methacloryloxy-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 diphenylamines (trade name: Sumilizer 9A), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-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-butanetetracarboxylate (trade name: LA-57), tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate (trade name: LA-52), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name: LA-62), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name: LA-67), mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol Examples of such esters include a mixed ester 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-63P), a mixed ester 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), (2,2,6,6-tetramethylene-4-piperidyl)-2-propylene carboxylate (trade name: Adeka STAB LA-82), and (1,2,2,6,6-pentamethyl-4-piperidyl)-2-propylene carboxylate (trade name: Adeka STAB LA-87).

[0075] The content of the component (E) is not particularly limited as long as it does not impair the effects of the present invention, but when it is contained, it is preferably 0.01 to 1 mass % in the photosensitive resin composition of the present invention. The antioxidant of the component (E) may be used alone or in combination of two or more kinds.

[0076] [Other additives] The photosensitive resin composition of the present invention may contain other additives in addition to the above-mentioned components. Examples of the additives include surfactants commonly used to improve coatability.

[0077] The surfactant is preferably a nonionic one, and examples thereof include fluorine-based surfactants, specifically perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, fluorine-containing organosiloxane compounds, etc. Commercially available surfactants can be used, such as 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), and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad "FC-430" and "X-70-093" are preferred. The content of the surfactant is not particularly limited as long as it does not impair the effects of the present invention, but when it is contained, the content is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention.

[0078] A silane coupling agent can also be used as an additive. By including a silane coupling agent, the adhesion of the photosensitive resin composition to the adherend can be further improved. Examples of the silane coupling agent include an epoxy silane coupling agent and an aromatic-containing amino silane coupling agent. 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 it does not impair the effects of the present invention, but when it is included, it is preferably 0.01 to 5 mass% in the photosensitive resin composition of the present invention.

[0079] The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but may be, for example, a method in which the components described above are stirred and mixed, and then, if necessary, filtered through a filter or the like to remove solids.

[0080] [Pattern formation method] The pattern forming method of the present invention uses the photosensitive resin composition, (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition; (ii) exposing the photosensitive resin film to light; and (iii) developing the exposed photosensitive resin film with a developer This method makes it possible to obtain a fine pattern.

[0081] Step (i) is a step of forming a photosensitive resin film on a substrate using the photosensitive resin composition, such as a silicon wafer, a glass wafer, a quartz wafer, a plastic circuit board, a ceramic circuit board, etc.

[0082] The photosensitive resin film can be formed by a known method. For example, the photosensitive resin composition can be applied to a substrate by a dip method, a spin coating method, a roll coating method, or the like. The amount of the coating can be appropriately selected depending on the purpose, but an amount that results in a film thickness of 0.1 to 100 μm is preferable.

[0083] Here, in order to efficiently carry out the photocuring reaction, the solvent and the like may be evaporated in advance by preheating as necessary. Preheating can be carried out, for example, at 40 to 160° C. for about 1 minute to 1 hour.

[0084] Next, in step (ii), the photosensitive resin film is exposed to light. At this time, it is preferable to expose to light having a wavelength of 240 to 500 nm. Examples of the light having a wavelength of 240 to 500 nm include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line and i-line, and far ultraviolet light (248 nm). The exposure dose is 10 to 5,000 mJ / cm. 2 is preferred.

[0085] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out. The photomask is preferably made of a material that blocks light having a wavelength of 240 to 500 nm, and is preferably made of, for example, chromium, but is not limited thereto.

[0086] Furthermore, in order to enhance the development sensitivity, post-exposure bake (PEB) may be performed, for example, at 40 to 160° C. for 5 to 30 minutes.

[0087] Step (iii) is a step of developing the photosensitive resin film using a developer after exposure or PEB. The developer is preferably an organic solvent-based developer used as a solvent, such as isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. By developing using the organic solvent-based developer, a negative pattern in which the non-exposed area is dissolved and removed can be obtained. Development can be performed by a normal method, such as immersing the substrate on which the pattern is formed in the developer. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a film having a desired pattern.

[0088] The method for forming a pattern is as described above. However, when it is not necessary to form a pattern, for example when it is desired to simply form a uniform film, in step (ii) of the pattern formation method, a film can be formed by exposing to light of an appropriate wavelength without using the photomask.

[0089] Furthermore, if necessary, (iv) the film on which the pattern is formed may be further heated in an oven or on a hot plate at 80 to 300°C for about 10 minutes to 10 hours to increase the crosslink density and remove any remaining volatile components (post-curing).

[0090] [Optical semiconductor element] By forming a fine pattern by the method using the photosensitive resin composition, an optical semiconductor element can be manufactured. In addition, the film obtained from the photosensitive resin composition has excellent transparency, light resistance, and heat resistance, and an optical semiconductor element having the film is suitably used for optical devices such as light emitting elements such as light emitting diodes, light receiving elements such as photodiodes, optical sensors, and CMOS image sensors, and optical transmission devices such as optical waveguides. The film preferably has a transmittance of 92% or more, more preferably 96% or more, and particularly preferably 98% or more, for light with a wavelength of 400 nm. EXAMPLES

[0091] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, Mw was measured by GPC using a TSKGEL Super HZM-H (manufactured by Tosoh Corporation) as a GPC column under analysis conditions of a flow rate of 0.6 mL / min, an elution solvent of THF, and a column temperature of 40° C., with monodisperse polystyrene as the standard.

[0092] [1] Polymer synthesis and evaluation The compounds used in the synthesis of the polymer are shown below. [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [Example 1-1] Synthesis of Polymer 1 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 53.0g (0.20 mol) of the compound represented by formula (S-2), 48.1g (0.40 mol) of the compound represented by formula (S-3a), and 85.7g (0.40 mol) of the compound represented by formula (S-4a) were added, and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 1. The Mw of polymer 1 was 16,000. The polymer 1 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0098] [Example 1-2] Synthesis of Polymer 2 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 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, and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 2. The Mw of polymer 2 was 15,000. The polymer 2 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0099] [Example 1-3] Synthesis of Polymer 3 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 92.8g (0.35 mol) of the compound represented by formula (S-2), 56.8g (0.35 mol) of the compound represented by formula (S-3b), and 64.3g (0.30 mol) of the compound represented by formula (S-4a) were added, and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 3. The Mw of polymer 3 was 12,000. The polymer 3 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0100] [Examples 1-4] Synthesis of Polymer 4 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 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, and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 4. The Mw of polymer 4 was 13,000. The polymer 4 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0101] [Examples 1-5] Synthesis of Polymer 5 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 53.0g (0.20 mol) of the compound represented by formula (S-2), 24.0g (0.20 mol) of the compound represented by formula (S-3a), and 103g (0.60 mol) of the compound represented by formula (S-4b) were added, followed by adding 700g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (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 of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 5. The Mw of polymer 5 was 9,000. The polymer 5 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0102] [Examples 1-6] Synthesis of Polymer 6 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 79.5g (0.30 mol) of the compound represented by formula (S-2), 32.5g (0.20 mol) of the compound represented by formula (S-3b), and 86.1g (0.50 mol) of the compound represented by formula (S-4b) were added, and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 6. The Mw of polymer 6 was 8,000. The polymer 6 was 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained repeating units represented by formula (A1), repeating units represented by formula (A2) and repeating units represented by formula (A3).

[0103] [Examples 1-7] Synthesis of Polymer 7 In a 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 106 g (0.40 mol) of the compound represented by formula (S-2) and 129 g (0.60 mol) of the compound represented by formula (S-4a) were added, followed by adding 700 g of toluene and heating to 70°C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5 mass%) was added, and 192 g (0.99 mol) of the compound represented by formula (S-1) was added dropwise over 1 hour (total of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition was completed, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain polymer 7. The Mw of polymer 7 was 11,000. The polymer 7 was obtained by 1 It was confirmed by 1 H-NMR (Bruker) that the polymer contained a repeating unit represented by formula (A1) and a repeating unit represented by formula (A3).

[0104] [Comparative Example 1-1] Synthesis of Comparative Polymer 1 A 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 53.0g (0.20 mol) of the compound represented by formula (S-2), 48.1g (0.40 mol) of the compound represented by formula (S-3a) and 56.5g (0.40 mol) of the compound represented by formula (S-5a), and then 700g of toluene was added and heated to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (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 of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain a comparative polymer 1. The Mw of the comparative polymer 1 was 10,000.

[0105] [Comparative Example 1-2] Synthesis of Comparative Polymer 2 A 10L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser was charged with 92.8g (0.35 mol) of the compound represented by formula (S-2), 56.8g (0.35 mol) of the compound represented by formula (S-3b), and 59.8g (0.30 mol) of the compound represented by formula (S-5b), and then 700g of toluene was added and 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 of hydrosilyl groups: total of alkenyl groups = 0.99: 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 8 hours, and then toluene was distilled off from the reaction solution under reduced pressure to obtain comparative polymer 2. The Mw of comparative polymer 2 was 12,000.

[0106] [Light transmission test 1] Polymers 1 to 7 and comparative polymers 1 and 2 were each dissolved in cyclopentanone to a concentration of 50% by mass to prepare a polymer solution. Each polymer solution was applied onto a glass substrate, heated at 60°C for 30 minutes, and then heated at 190°C for 2 hours in a nitrogen atmosphere to prepare a film (thickness 10 μm). The transmittance of light with a wavelength of 400 nm was measured for each of the obtained films. The results are shown in Table 1. The film thickness was measured using an optical interference film thickness measuring device manufactured by SCREEN, and was the film thickness of a film previously formed on a silicon wafer under the same conditions.

[0107] [Table 1]

[0108] [Light transmission test 2] A sample consisting of the coating on a glass wafer obtained by the above method was continuously irradiated with a 400 nm, 1 W laser in an oven at 50°C, and the rate of change in light transmittance after 100 hours and 1,000 hours was measured, with the initial value (before laser irradiation) being taken as 100%. The results are shown in Table 2.

[0109] [Table 2]

[0110] [Curing temperature measurement test 1] To 100 parts by mass of polymers 1 to 7 and comparative polymers 1 and 2, 3 parts by mass of CPI-210S (manufactured by San-Apro Co., Ltd.) was added as a photoacid generator, and cyclopentanone was added so that the solid concentration became 50% by mass, and the mixture was dissolved until it was uniform. 2 g of each solution was placed in an aluminum petri dish, and the solution was dried by heating at a temperature of 100°C for 15 minutes. After exposing the remaining solid to 3,000 mJ of 365 nm light, differential scanning calorimetry was performed, and the curing temperature was evaluated based on the exothermic peak. The results are shown in Table 3. The differential scanning calorimetry was performed using a Q2000 from TA Instruments, and the curing temperature was measured by increasing the temperature from 0°C to 200°C at a rate of 10°C per minute.

[0111] [Table 3]

[0112] [2] Preparation and evaluation of photosensitive resin composition [Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-8] Photosensitive resin compositions were prepared by mixing polymers 1 to 7 as component (A), comparative polymers 1 and 2, photoacid generators B-1 and B-2 as component (B), crosslinkers C-1, C-2 and C-3 as component (C), and cyclopentanone (CP) as a solvent for component (D) in the compositions shown in Tables 4 and 5 below, stirring to dissolve, and then microfiltration using a 0.2 μm Teflon (registered trademark) filter.

[0113] [Table 4]

[0114] [Table 5]

[0115] In Tables 4 and 5, the photoacid generators B-1 and B-2, and the crosslinking agents C-1, C-2 and C-3 are as follows. Photoacid generators B-1 and B-2: [ka] (In the formula, Rf is a perfluoroalkyl group, and b is 0 to 6.)

[0116] Crosslinking agents C-1, C-2, C-3: [ka]

[0117] [Pattern formation evaluation] Each photosensitive resin composition was coated on an 8-inch silicon wafer primed with hexamethyldisilazane to a thickness of 10 μm using a spin coater. In order to remove the solvent from the composition, the wafer was placed on a hot plate, heated at 110° C. for 3 minutes, and dried. In order to form a line-and-space pattern and a contact hole pattern on the obtained photosensitive resin film, the wafer was exposed to light through a mask using a contact aligner type exposure device under exposure conditions of 365 nm. After light irradiation, PEB was performed on a hot plate at 120° C. for 3 minutes, and then cooled, and the wafer was spray-developed with propylene glycol monomethyl ether acetate (PGMEA) for 300 seconds to form a pattern.

[0118] The photosensitive resin film on the wafer on which the pattern was formed by the above method was post-cured in an oven at 190°C for 2 hours while purging with nitrogen. Then, the cross sections of the formed contact hole patterns of 50μm, 30μm, 20μm, 10μm, and 5μm were observed by a scanning electron microscope (SEM), and the smallest hole pattern in which the hole penetrated to the bottom of the film was determined as the limiting resolution. Furthermore, the perpendicularity of the 50μm contact hole pattern was evaluated from the obtained cross-sectional photograph, and a perpendicular pattern was rated as ◎, a slightly inverted tapered shape was ◯, a reverse tapered shape was △, and an opening failure was rated as ×. The results are shown in Tables 6 and 7.

[0119] [Table 6]

[0120] [Table 7]

[0121] [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 and heated at 110° C. for 3 minutes to dry. The entire surface of the composition coated on the glass wafer was irradiated with light from a high-pressure mercury lamp (wavelength 360 nm) without a mask using a mask aligner MA8 from SUSS MicroTec, and then PEB was performed and the wafer was immersed in PGMEA. The film remaining after this operation was further heated in an oven at 190° C. for 2 hours to obtain a film. The transmittance of light with a wavelength of 400 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 8 and 9.

[0122] [Table 8]

[0123] [Table 9]

[0124] [Light transmission test 2] A sample consisting of the coating on a glass wafer obtained by the above method was continuously irradiated with a 400 nm laser of 1 W in an oven at 50° C., and the rate of change in light transmittance after 100 hours and 1,000 hours was measured, with the initial value (before laser irradiation) being taken as 100%. The results are shown in Tables 10 and 11.

[0125] [Table 10]

[0126] [Table 11]

[0127] [Curing temperature measurement test] 2 g of each photosensitive resin composition was placed in an aluminum petri dish, heated at 100°C for 15 minutes, and dried. The remaining solid was exposed to 3,000 mJ of 365 nm light, and then differential scanning calorimetry was performed to evaluate the curing temperature based on the exothermic peak. The differential scanning calorimetry was performed using a TA Instruments Q2000, and the curing temperature was measured by increasing the temperature from 0°C to 200°C at a rate of 10°C per minute. The results are shown in 12 and 13.

[0128] [Table 12]

[0129] [Table 13]

[0130] From the above results, the polymer of the present invention, which contains a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxyl-substituted alkyl ether skeleton in the main chain and an epoxy group in the side chain, is excellent in low-temperature curing properties. In addition, the film obtained from the polymer of the present invention is a film with high transparency and high light resistance. Furthermore, the photosensitive resin composition containing the polymer of the present invention can be microfabricated, has excellent low-temperature curing properties, and gives a film with high transparency and high light resistance.

Claims

1. A polymer containing a silphenylene skeleton, an isocyanuric acid skeleton, and a hydroxyl group-substituted alkyl ether skeleton in its main chain and containing an epoxy group in its side chain, A polymer comprising 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). 【Chemistry 1】 (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. X 1 is a divalent group represented by formula (X1) below. X 2 is a divalent group represented by formula (X2) below. X 3 is a divalent group represented by formula (X3) below.) 【Chemistry 2】 (In the formula, R 11 and R 12 are each independently a hydrogen atom or a methyl group. R 13 is a hydrocarbylene group having 1 to 8 carbon atoms, and an ester bond or an ether bond may be present between the carbon-carbon bonds. n 1 and n 2 are each independently an integer of 0 to 7. The dashed lines represent bonds.) 【Chemistry 3】 (In the formula, R 21 and R 22 each independently represent a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. m represents an integer of 0 to 10. The dashed lines represent bonds.) 【Chemistry 4】 (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 hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom, and when R 33 is a saturated hydrocarbyl group, it may contain a primary or secondary alcoholic hydroxy group as a substituent. R 34 is a hydroxy group or a saturated hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom, and when R 34 is a saturated hydrocarbyl group, it may contain a primary or secondary alcoholic hydroxy group as a substituent. When R 33 is a hydrogen atom and R 34 is a saturated hydrocarbyl group, R 34 contains at least one primary or secondary alcoholic hydroxy group as a substituent. When R 33 and R 34 are both saturated hydrocarbyl groups, one or both of them contain at least one primary or secondary alcoholic hydroxy group as a substituent. p 1 and p 2 are each independently an integer from 1 to 7. q 1 and q 2 are each independently an integer from 1 to 7. The dashed lines represent bonds.

2. The polymer according to claim 1, wherein the divalent group represented by formula (X3) contains 9 to 20 carbon atoms.

3. 3. The polymer according to claim 1, wherein a, b and c are positive numbers satisfying 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.

4. R 34 The polymer according to any one of claims 1 to 3, wherein is a linear alkyl group having a hydroxyl group at the terminal.

5. R 31 and R 32 The polymer according to any one of claims 1 to 4, wherein is a hydrogen atom.

6. p 1 and p 2 The polymer according to any one of claims 1 to 5, wherein

7. q 1 and q 2 The polymer according to any one of claims 1 to 6, wherein

8. 8. The polymer according to claim 1, wherein a 10 μm-thick film made of the polymer has a transmittance of 95% or more for light having a wavelength of 400 nm.

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

10. The photosensitive resin composition according to claim 9, further comprising (C) a cationic polymerizable crosslinking agent.

11. (i) forming a photosensitive resin film on a substrate using the photosensitive resin composition according to claim 9 or 10; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film using a developer. A pattern forming method comprising the steps of:

12. A method for manufacturing an optical semiconductor element provided with a photosensitive resin film, comprising the pattern forming method according to claim 11.

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