Photosensitive resin composition, pattern forming method and anti-reflection film

Abstract

The present invention relates to a photosensitive resin composition, a pattern forming method and an anti-reflection film. The present invention provides a photosensitive resin composition comprising (A) an organosilicon resin containing an acid-crosslinkable group, (B) a photoacid generator, and (C) hollow silica. The photosensitive resin composition has satisfactory reliability, flexibility, photolithography resolution and light resistance while maintaining the function of an anti-reflection film.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This nonprovisional application claims priority under 35 U.S.C. 119(a) to Patent Application No. 2018-216419 filed in Japan on November 19, 2018, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a photosensitive resin composition, a pattern forming method and an antireflection film. Background Art

[0004] With the widespread use of optical devices, it is now necessary to impart certain optical properties to transparent materials, typically by forming an anti-reflection film on its surface to impart an anti-reflection function. Although anti-reflection films are usually formed by evaporation or sputtering, there is an increasing demand for anti-reflection films formed by inexpensive wet coating techniques. In wet coating, organic hard coating agents such as acrylic resins and hard coating agents such as silane compounds are used.

[0005] It is often necessary to have an anti-reflection film with low reflectivity. By dispersing hollow silicon dioxide particles as a low reflectivity material in a matrix to be prepared into a film composition, applying and curing the composition, the technology of forming a transparent film with low reflectivity is known (see patent documents 1 and 2). In addition to low reflectivity, anti-reflection film must also meet some other requirements. One requirement is sufficient film strength to improve reliability. The second requirement is the micro-processing capability of the film, because more optical devices require micro-manufacturing. The third requirement is that the film tolerates discoloration caused by light from high-power optical devices.

[0006] Citation List

[0007] Patent Document 1: JP-A 2012-137636

[0008] Patent Document 2: JP-A 2003-292831 Summary of the invention

[0009] The present invention aims to provide a photosensitive resin composition having satisfactory reliability (adhesion and crack resistance), flexibility, photolithography resolution and light resistance while maintaining the function of an anti-reflection film. Another object is to provide a pattern forming method using the photosensitive resin composition and a cured film of the photosensitive resin composition having an anti-reflection function.

[0010] The present inventors have found that a photosensitive resin composition comprising a silicone resin having acid-crosslinkable groups, a photoacid generator, and hollow silica is easy to form a film, and the resulting film exhibits improved light resistance and improved microfabrication properties such as resolution, and thus has satisfactory reliability (adhesion and crack resistance) and flexibility while maintaining the function of an antireflection film.

[0011] In one aspect, the present invention provides a photosensitive resin composition comprising (A) a silicone resin having acid-crosslinkable groups, (B) a photoacid generator, and (C) hollow silica.

[0012] Typically, the acid-crosslinkable group is an epoxy group, an oxetanyl group, or a vinyl ether group.

[0013] In a preferred embodiment, component (A) is a silicone resin comprising repeating units having the following formulas (A1) to (A6).

[0014]

[0015] Wherein, R 1 to R 4 are each independently a C1-C 20 monovalent hydrocarbon group which may contain a heteroatom, m is each independently an integer from 1 to 600, provided that when m is an integer of at least 2, the groups R 3 may be the same or different and the groups R 4 may be the same or different, and a, b, c, d, e, and f are numbers in the following ranges: 0≤a≤1, 0≤b≤1, 0≤c≤1, 0≤d≤1, 0≤e≤1, 0≤f≤1, 0<c+d+e+f≤1 and a+b+c+d+e+f = 1.

[0016] X 1 is a divalent group having the formula (X1):

[0017]

[0018] Wherein, R 11 to R 14 are each independently a C1-C 20 monovalent hydrocarbon group which may contain a heteroatom, p is an integer from 1 to 600, provided that when p is an integer of at least 2, the groups R 13 may be the same or different and the groups R 14 may be the same or different, R 15 and R 16 are each independently hydrogen or methyl, and x is each independently an integer from 0 to 7.

[0019] X 2 is a divalent group having the formula (X2):

[0020]

[0021] Among them, Y 1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group, R 21 and R 22 are each independently C1-C4 alkyl or alkoxy, provided that when g is 2, the group R 21 can be the same or different. When h is 2, the group R 22 Can be the same or different, R 23 and R 24 Each is independently hydrogen or methyl, y is each independently an integer from 0 to 7, and g and h are each independently 0, 1 or 2.

[0022] X 3 is a divalent group having the formula (X3):

[0023]

[0024] Among them, R 31 and R 32 are each independently hydrogen or methyl, z is each independently an integer from 0 to 7, R 33 is a C1-C8 monovalent hydrocarbon group which may contain an ester bond or an ether bond, or a monovalent group having the formula (X3-1):

[0025]

[0026] Among them, R 34 It is a C1-C8 divalent hydrocarbon group which may contain an ester bond or an ether bond.

[0027] In a preferred embodiment, the hollow silica (C) has an average particle size of at most 1 μm. Also preferably, the hollow silica (C) is present in an amount of 20 to 90% by weight of the composition.

[0028] The photosensitive resin composition may further contain (D) a crosslinking agent, (E) an antioxidant and / or (F) a solvent.

[0029] In another aspect, the present invention provides a pattern forming method comprising the steps of:

[0030] (i) applying the photosensitive resin composition defined above onto a substrate to form a photosensitive resin film thereon,

[0031] (ii) exposing the photosensitive resin film to radiation, and

[0032] (iii) The exposed resin film is developed with a developer.

[0033] In a further aspect, the present invention provides a method for preparing an anti-reflection film, comprising the pattern forming method defined above, the anti-reflection film comprising a patterned photosensitive resin film.

[0034] In a further aspect, the present invention provides an anti-reflection film comprising the photosensitive resin composition defined above.

[0035] Also contemplated herein are articles comprising the anti-reflective film defined above.

[0036] Beneficial Effects of the Invention

[0037] A photosensitive resin composition comprising a specific acid-crosslinkable group-containing silicone resin, a photoacid generator and hollow silica can be effectively coated to form a film, which functions as an antireflection film, exhibits light resistance and improved micromachining properties such as resolution, and thus has satisfactory reliability (adhesion and crack resistance) and flexibility. DETAILED DESCRIPTION

[0038] As used herein, the notation (Cn-Cm) means a group containing n to m carbon atoms per group. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and the description includes instances where the event or circumstance occurs as well as instances where it does not. PAG means photoacid generator.

[0039] Photosensitive resin composition

[0040] One embodiment of the present invention is a photosensitive resin composition including (A) an acid-crosslinkable group-containing silicone resin, (B) a photoacid generator, and (C) hollow silica.

[0041] (A) Silicone resin containing acid-crosslinkable groups

[0042] The organosilicon resin containing an acid-crosslinkable group as component (A) is a resin having a siloxane structure of an acid-crosslinkable group. As used herein, an acid-crosslinkable group refers to a group that can form a chemical bond under the action of an acid. Preferred examples of acid-crosslinkable groups include epoxy, oxetane and vinyl ether groups, of which epoxy is the most preferred.

[0043] The silicone resin as component (A) is preferably an epoxy-containing silicone resin comprising repeating units having the following formulae (A1) to (A6) (referred to simply as repeating units (A1) to (A6)).

[0044]

[0045] In formulas (A2), (A4) and (A6), R 1 To R 4 Each independently is a C1-C 20 monovalent hydrocarbon group, and m is each independently an integer from 1 to 600. When m is an integer of at least 2, the group R 3 can be the same or different and the groups R 4 In repeating units (A2), (A4) and (A6), when at least two siloxane units are included, the siloxane units may all be the same or may include at least two different siloxane units. When at least two different siloxane units are included (i.e., m is an integer of at least 2), the siloxane units may be randomly or alternately bonded, or may include a plurality of blocks each consisting of the same siloxane unit.

[0046] The monovalent hydrocarbon group may be linear, branched or cyclic, and includes monovalent aliphatic hydrocarbon groups such as C1-C 20 Alkyl and C2-C 20 Alkenyl, and monovalent aromatic hydrocarbon groups, such as C6-C 20 Aryl and C7-C 20 Aralkyl.

[0047] Suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, norbornyl and adamantyl. Suitable alkenyl groups include vinyl, propenyl, butenyl and pentenyl.

[0048] The monovalent aliphatic hydrocarbon group may contain heteroatoms. Specifically, in the monovalent aliphatic hydrocarbon group, some or all of the hydrogen atoms may be replaced by halogen atoms such as fluorine, chlorine, bromine and iodine, or a carbonyl moiety, an ether bond or a thioether bond may be inserted between carbon atoms. A typical aliphatic hydrocarbon group containing heteroatoms is 2-oxocyclohexyl.

[0049] Suitable aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, naphthyl, biphenyl and terphenyl. Suitable aralkyl groups include benzyl and phenethyl.

[0050] The monovalent aromatic hydrocarbon group may contain heteroatoms. Specifically, some or all of the hydrogen atoms may be replaced by C1-C 10 Alkoxy, C1-C 10 Alkylthio, C6-C 20 Aryloxy or C6-C 20 Arylthio substitution.

[0051] Suitable C1-C10 The alkoxy group includes methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropyloxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutyloxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, norbornyloxy and adamantyloxy.

[0052] Suitable C1-C 10 The alkylthio group includes methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, cyclobutylthio, n-pentylthio, cyclopentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, norbornylthio and adamantylthio.

[0053] Suitable C6-C 20 The aryloxy group includes phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-ethylphenoxy, 3-ethylphenoxy, 4-ethylphenoxy, 4-tert-butylphenoxy, 4-butylphenoxy, dimethylphenoxy, naphthoxy, biphenyloxy and terphenyloxy.

[0054] Suitable C6-C 20 The arylthio group includes a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-ethylphenylthio group, a 3-ethylphenylthio group, a 4-ethylphenylthio group, a 4-tert-butylphenylthio group, a 4-butylphenylthio group, a dimethylphenylthio group, a naphthylthio group, a biphenylthio group and a terphenylthio group.

[0055] Suitable substituted aryl groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, biphenyloxyphenyl and biphenylthiophenyl.

[0056] The monovalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. The monovalent aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

[0057] In the above groups, R 1 To R 4 It is preferably selected from methyl, ethyl, n-propyl and phenyl, more preferably methyl and phenyl.

[0058] In formulae (A2), (A4) and (A6), m is an integer of 1 to 600, preferably 1 to 300, and more preferably 1 to 100, each independently.

[0059] In formulas (A1) to (A6), a, b, c, d, e, and f are numbers within the following ranges: 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0 ≤ d ≤ 1, 0 ≤ e ≤ 1, 0 ≤ f ≤ 1, 0 < c + d + e + f ≤ 1 and a + b + c + d + e + f = 1; preferably 0.2 ≤ a + c + e ≤ 0.95, 0.05 ≤ b + d + f ≤ 0.8, 0 ≤ a + b ≤ 0.9, 0 ≤ c + d ≤ 0.7, 0 < e + f ≤ 1 and a + b + c + d + e + f = 1; more preferably 0.3 ≤ a + c + e ≤ 0.9, 0.1 ≤ b + d + f ≤ 0.7, 0 ≤ a + b ≤ 0.6, 0 ≤ c + d ≤ 0.4, 0.4 ≤ e + f ≤ 1 and a + b + c + d + e + f = 1.

[0060] In formulas (A1) and (A2), X 1 is a divalent group having formula (X1).

[0061]

[0062] In formula (X1), R 11 to R 14 are each independently a C1-C 20 monovalent hydrocarbon group which may contain a heteroatom, and p is an integer from 1 to 600. When p is an integer of at least 2, the groups R 13 may be the same or different and the groups R 14 may be the same or different. R 15 and R 16 are each independently hydrogen or methyl, and x is each independently an integer from 0 to 7. In the group of formula (X1), when including at least two siloxane units, the siloxane units may all be the same or may include at least two different siloxane units. When including at least two different siloxane units (i.e., p is an integer of at least 2), the siloxane units may be bonded randomly or alternately, or may include a plurality of blocks each composed of the same siloxane units.

[0063] The monovalent hydrocarbon group which may contain a heteroatom may be linear, branched or cyclic and examples thereof are as exemplified above for R 1 to R 4 . Among them, R 11 to R 14 are preferably selected from methyl, ethyl, n-propyl and phenyl, more preferably methyl and phenyl.

[0064] In formulas (A3) and (A4), X 2 is a divalent group having formula (X2).

[0065]

[0066] In formula (X2), Y1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 21 and R 22 Each is independently a C1-C4 alkyl or alkoxy group, and g and h are each independently 0, 1 or 2. When g is 2, the group R 21 can be the same or different. When h is 2, the group R 22 Can be the same or different. 23 and R 24 Each of them is independently hydrogen or methyl, and each of them is independently an integer from 0 to 7.

[0067] In formulas (A5) and (A6), X 3 is a divalent group having the formula (X3).

[0068]

[0069] In formula (X3), R 31 and R 32 are each independently hydrogen or methyl, and z is each independently an integer from 0 to 7.

[0070] In formula (X3), R 33 It is a C1-C8 monovalent hydrocarbon group which may contain an ester bond or an ether bond, or a monovalent group having the formula (X3-1).

[0071]

[0072] The monovalent hydrocarbon group can be straight chain, branched or cyclic and its examples include alkyl groups such as methyl, ethyl and n-propyl, and aryl groups such as phenyl. Methyl and phenyl are especially preferred, with methyl being the most preferred. In the monovalent group, an ester bond or an ether bond can be inserted between carbon atoms.

[0073] In formula (X3-1), R 34 It is a C1-C8 divalent hydrocarbon group that may contain an ester bond or an ether bond. The divalent hydrocarbon group may be linear, branched or cyclic and examples thereof include alkane diyls such as methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl and butane-1,4-diyl. Among them, methylene and ethylene are preferred, and methylene is most preferred. In the divalent hydrocarbon group, an ester bond or an ether bond may be inserted between carbon atoms.

[0074] R 33 It is preferably a methyl group, a phenyl group or a glycidyl group, and more preferably a methyl group or a glycidyl group.

[0075] The repeating units (A1) to (A6) may be bonded randomly or in blocks. The silicone resin containing acid-crosslinkable groups preferably has a silicone (siloxane unit) content of 30 to 80% by weight.

[0076] The acid-crosslinkable group-containing silicone resin preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. Throughout this disclosure, Mw is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent relative to polystyrene standards.

[0077] The silicone resin (A) can be prepared, for example, in a standard manner by mixing the necessary amounts of a vinyl-containing compound and a hydrosilyl-containing organosilicon compound (corresponding to the relevant proportions in the silicone resin) and carrying out a hydrosilylation reaction.

[0078] The acid-crosslinkable group-containing silicone resin may be used alone or in combination of two or more.

[0079] (B) Photoacid Generator

[0080] As the photoacid generator of component (B), there is no particular limitation, as long as it decomposes and generates acid when exposed to light, preferably it decomposes and generates acid when exposed to light of wavelength 190 to 500nm.PAG (B) serves as a curing catalyst.Suitable PAGs include onium salts, diazomethane derivatives, oxadioxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate derivatives, iminosulfonate derivatives, sulfonic acid oxime ester derivatives, iminosulfonate derivatives and triazine derivatives.

[0081] Exemplary onium salts include sulfonium salts having formula (B1) and iodonium salts having formula (B2).

[0082]

[0083] In formulas (B1) and (B2), R 101 To R 105 are each independently an optionally substituted C1-C 12 Alkyl, optionally substituted C6-C 12 Aryl or optionally substituted C7-C 12 Aralkyl. - It is a non-nucleophilic counter ion.

[0084] Alkyl groups may be straight chain, branched or cyclic and include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl. Aryl groups include phenyl, naphthyl and biphenyl. Aralkyl groups include benzyl and phenethyl. Suitable substituents on these groups include oxo, straight chain, branched or cyclic C1-C 12 Alkoxy, linear, branched or cyclic C1-C 12 Alkyl, C6-C 24 Aryl, C7-C 25 Arylalkyl, C6-C 24 Aryloxy and C6-C 24 Arylthio.

[0085] R 101 To R 105 Preferred examples include optionally substituted alkyl groups such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl and 2-oxocyclohexyl; optionally substituted aryl groups such as phenyl, naphthyl, biphenyl, o-methoxyphenyl, m-methoxyphenyl or p-methoxyphenyl, ethoxyphenyl, m-tert-butoxyphenyl or p-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyl, oxyphenyl and biphenylthiophenyl; and optionally substituted aralkyl groups such as benzyl and phenethyl. More preferred among these are optionally substituted aryl groups and optionally substituted aralkyl groups.

[0086] Examples of non-nucleophilic counterions include halide ions such as chloride and bromide; fluoroalkanesulfonate ions such as trifluoromethanesulfonate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; arylsulfonate ions such as toluenesulfonate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkanesulfonate ions such as methanesulfonate and butanesulfonate; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methyl anion; and borate ions such as tetraphenylborate and tetrakis(pentafluorophenyl)borate.

[0087] Exemplary diazomethane derivatives include compounds having formula (B3).

[0088]

[0089] In formula (B3), R 111 and R 112 Each independently is C1-C 12 Alkyl or haloalkyl, optionally substituted C6-C 12Aryl or C7-C 12 Aralkyl.

[0090] The alkyl group may be linear, branched or cyclic and may be, for example, 101 To R 105 Examples of the halogenated alkyl group include alkyltrifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl and nonafluorobutyl.

[0091] Examples of optionally substituted aryl groups include phenyl; alkoxyphenyl groups such as 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl or 4-ethoxyphenyl, 3-tert-butoxyphenyl or 4-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, 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.

[0092] Exemplary glyoxime derivatives include compounds having formula (B4).

[0093]

[0094] In formula (B4), R 121 To R 124 Each independently is C1-C 12 Alkyl or haloalkyl, optionally substituted C6-C 12 Aryl or C7-C 12 Aralkyl. 123 and R 124 can be bonded together to form a ring with the carbon atoms to which they are attached. In the case of a ring, R 123 With R 124 Bonding to form C1-C 12 A straight chain or branched chain alkylene group.

[0095] Examples of alkyl, haloalkyl, optionally substituted aryl and aralkyl are as described above for R 111 and R 112 Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0096] 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)phenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetra(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetra(fluorophenyl)borate, triphenylsulfonium tetra(pentafluorophenyl)borate, and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetra(pentafluorophenyl)borate.

[0097] Examples of diazomethane derivatives 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, and bis(n-propylsulfonyl)diazomethane. 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 and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

[0098] Examples of 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-pentanedioneglyoxime, bis-O-(p-toluenesulfonyl)-2-methyl-3,4- Pentanedione glyoxime, bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, bis-O-(n-butanesulfonyl)-α-diphenylglyoxime, bis-O-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-O-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-O-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime , bis-O-(methanesulfonyl)-α-dimethylglyoxime, bis-O-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-O-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-O-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-O-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-O-(cyclopentanesulfonyl)-α-dimethylglyoxime bis-O-(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 and bis-O-(camphorsulfonyl)-α-dimethylglyoxime.

[0099] Examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0100] Examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0101] Examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0102] Examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0103] Examples of the iminosulfonate derivatives include phthalimido trifluoromethanesulfonate, phthalimido toluenesulfonate, 5-norbornene-2,3-dicarboximido trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido toluenesulfonate, 5-norbornene-2,3-dicarboximido n-butylsulfonate and N-trifluoromethylsulfonyloxynaphthyl imide.

[0104] A typical sulfonic acid oxime ester derivative is α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile.

[0105] Examples of the imidosulfonate 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 and 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane.

[0106] As PAG, onium salts are preferred, and sulfonium salts are more preferred.

[0107] Preferably, PAG (B) is used in an amount of 0.05 to 20 parts by weight, more preferably 0.2 to 5 parts by weight per 100 parts by weight of component (A). The amount of PAG within the range ensures sufficient photocurability. In order to obtain the transparency and light resistance characteristics of the present invention, the amount of light-absorbing PAG (B) is as small as possible within the range of ensuring photocurability. PAGs can be used alone or in combination.

[0108] (C) Hollow Silica

[0109] Component (C) is hollow silica in the form of silica particles derived from a silicon compound or an organosilicon compound, ie, silica particles having spaces or pores on the surface and / or inside thereof. The hollow silica acts as a low refractive index agent to impart an antireflection effect to the cured film.

[0110] Hollow or vesicular silica can take spherical, chain, needle, disc, flake, rod, fiber or irregular shape, wherein spherical or needle shape is preferred. Spherical hollow silica should preferably have an average particle size of 1 to 1,000 nm, more preferably 5 to 500 nm, and even more preferably 10 to 100 nm. When the average particle size is within this range, spherical nanoparticles are effective for imparting transparency to the cured film. As used herein, the average particle size can be determined as a weight average value D by a particle size distribution measurement system based on a laser diffraction method. 50 (Particle diameter corresponding to 50% of the cumulative weight, or median diameter). The hollow silica may be in the form of crystals, sol or gel.

[0111] If necessary, the hollow silica may be surface-treated with a silane coupling agent and then used. Surface treatment is preferred because the surface-treated hollow silica is more compatible with the silicone resin (A). Thus, a cured film that is less prone to whitening and more transparent can be obtained.

[0112] Hollow silica is commercially available, for example under the trade name The silica organosol series is obtained from JGC C&C under the trade name The mesoporous silica of the series was obtained from Taiyo Kagaku Co., Ltd., and the The hollow silica of the Nittetsu series was obtained from Nittetsu Mining Co., Ltd.

[0113] The appropriate amount of component (C) is 20 to 90 weight %, more preferably 30 to 70 weight %, based on the total weight of components (A) to (C). When the amount of component (C) is at least 20wt%, a film with low refractive index and anti-reflection function can be obtained. When the amount of component (C) is at most 90wt%, there is no risk of composition loss of fluidity and becoming inconvenient to shape and leaving unfilled cavities or voids. Hollow silica as component (C) can be used alone or in combination.

[0114] (D) Cross-linking agent

[0115] The photosensitive resin composition may further include (D) a crosslinking agent. The crosslinking agent reacts with the epoxy group on the component (A) to promote pattern formation and serves to increase the strength of the photocured resin film.

[0116] The crosslinking agent is preferably selected from compounds having an average of at least two epoxy, alicyclic epoxy or oxetane groups per molecule. Such compounds are preferably low or high molecular weight compounds having an Mw of 100 to 20,000, more preferably 200 to 10,000. Compounds having an Mw of at least 100 provide sufficient photocuring, while compounds having an Mw of up to 20,000 do not deteriorate the heat resistance of the photocured composition.

[0117] The amount of component (D) is 0 to 100 parts by weight per 100 parts by weight of component (A), and when used, preferably 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight. When the amount of component (D) is at least 0.5 parts, sufficient curing upon exposure can be obtained. When the amount of component (D) is at most 100 parts, the share of component (A) in the composition is not so reduced that the cured composition exhibits the desired effect. Component (D) can be used alone or in combination.

[0118] (E) Antioxidants

[0119] The photosensitive resin composition may further contain (E) an antioxidant as an additive, which is effective for improving heat resistance. The antioxidant is preferably selected from hindered phenol compounds and hindered amine compounds.

[0120] Although the hindered phenol compound used herein is not particularly limited, the hindered phenol compounds listed below are preferred.

[0121] 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-butylhydroquinone (trade name Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name Nocrac M-17), 2,5-di-tert-amylhydroquinone (trade name Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (trade name Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid 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 Adeka Stab 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-methylcyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (trade name Seenox226M), 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-hydroxyhydrocinnamic acid amide) (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(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium / polyethylene wax 50 / 50 mixture (trade name IRGANOX 1425WL), 2-(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-butyl dibenzo[d,f][1,3,2]dioxaphosphepin (trade name Sumilizer GP), etc.

[0122] Although the hindered amine compound used herein is not particularly limited, the hindered amine compounds listed below are preferred.

[0123] p,p'-dioctyldiphenylamine (trade name IRGANOX 5057), phenyl-α-naphthylamine (trade name NocracPA), poly (2,2,4-trimethyl-1,2-dihydroquinoline) (trade name Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (trade name Nocrac TD), N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine (trade name Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name Antigene 6C), alkylated diphenylamine (trade name Sumilizer 9A), 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylsuccinic acid dimethyl ester condensation product (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)ethylenediamine-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), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate (trade name Tinuvin 144), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (trade name Tinuvin 765), tetra(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 mixture of 1,2,3,4-butanetetracarboxylic acid esterified with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (trade name LA-62), a mixture of 1,2,3,4-butanetetracarboxylic acid esterified with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (trade name LA-67), a mixture of 1,2,3,4-butanetetracarboxylic acid esterified with 1,2 , a mixture of esters of 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), a mixture of esters of 1,2,3,4-butanetetracarboxylic acid, 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-piperidinyl)-2-propylene carboxylate (trade name Adeka Stab LA-82), (1,2,2,6,6-pentamethyl-4-piperidinyl)-2-propylene carboxylate (trade name Adeka Stab LA-87), etc. ,

[0124] The amount of component (E) used is not particularly limited as long as the benefits of the invention are not impaired. When used, the amount of component (E) is preferably 0.01 to 1% by weight of the resin composition. Antioxidants may be used alone or in combination.

[0125] (F) Solvent

[0126] (F) A solvent may be added to the photosensitive resin composition to facilitate coating operation. The solvent (F) used herein is not particularly limited as long as the components (A) to (E) and other additives (described later) are soluble or dispersible therein.

[0127] Preferred solvents are organic solvents. Exemplary, non-limiting examples of organic solvents include ketones, such as cyclohexanone, cyclopentanone and methyl-2-n-amyl 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 (PGME), 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 (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, tert-butyl acetate, tert-butyl propionate and propylene glycol mono-tert-butyl ether acetate and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0128] Among these solvents, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone and mixtures thereof are preferred, in which PAG is most soluble.

[0129] From the viewpoint of viscosity and compatibility of the resin composition, the solvent (F) is preferably used in an amount of 200 to 20,000 parts by weight, more preferably 250 to 10,000 parts by weight, and particularly 350 to 3,500 parts by weight per 100 parts by weight of components (A) and (C) combined.

[0130] Other additives

[0131] In addition to the aforementioned components, the photosensitive resin composition may contain optional additives such as a surfactant generally used to improve coating properties, and a silane coupling agent.

[0132] Preferred surfactants are nonionic surfactants, such as fluorochemical surfactants, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amine oxides and fluorinated organosiloxane compounds. These surfactants are commercially available. Illustrative examples include 3M's FC-430, from AGC SeimiChemical Co., Ltd. S-141 and S-145 from Daikin Industries Ltd. DS-401, DS-4031 and DS-451 from DIC Corp. F-8151, and X-70-093 from Shin-Etsu Chemical Co., Ltd. Preferred surfactants are Fluorad FC-430 and X-70-093. The amount of the surfactant is not particularly limited as long as the benefits of the present invention are not affected. When used, the amount of the surfactant is preferably 0.01 to 1% by weight of the resin composition.

[0133] The introduction of silane coupling agents is effective for enhancing the adhesion of the resin composition to the adherend. Suitable silane coupling agents include epoxy silane coupling agents and aromatic amino silane coupling agents. The silane coupling agents can be used alone or in combination. As long as the benefits of the present invention are not affected, the amount of the silane coupling agent used is not particularly limited. When used, the amount of the silane coupling agent is preferably 0.01 to 5 weight % of the resin composition.

[0134] Patterning method

[0135] Another embodiment of the present invention is a method for forming a pattern using the photosensitive resin composition defined above, the method comprising the following steps:

[0136] (i) applying the photosensitive resin composition onto a substrate to form a photosensitive resin film thereon,

[0137] (ii) exposing the photosensitive resin film to radiation, and

[0138] (iii) The exposed resin film is developed with a developer.

[0139] In step (i), a photosensitive resin composition is applied onto a substrate to form a photosensitive resin film thereon. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, plastic circuit board substrates, and ceramic circuit board substrates.

[0140] The coating technique may be any well-known technique such as dip coating, spin coating and roll coating. The coating weight may be appropriately selected for a particular purpose, preferably so that a resin film having a thickness of 1 to 5,000 nm, more preferably 50 to 4,000 nm is formed.

[0141] For the purpose of improving the uniformity of the film thickness on the substrate surface, a pre-wetting technique can be used, that is, a drop of solvent can be applied to the substrate surface and then the photosensitive resin composition is applied. Preferred solvents include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether (PGME). The solvent used in the photosensitive resin composition can also be used for pre-wetting.

[0142] At this time, if necessary, for efficient photocuring reaction, the coating material may be pre-baked to evaporate the solvent, etc. The pre-baking may be performed, for example, at 40 to 140° C. for 1 minute to about 1 hour.

[0143] Next in step (ii), the photosensitive resin film is exposed to radiation. The exposure radiation preferably has a wavelength of 10 to 600nm, more preferably 190 to 500nm. Examples of radiation include radiation of various wavelengths from a unit emitting radiation, particularly UV radiation, such as g-line, h-line or i-line and deep UV (248nm, 193nm). Particularly preferred is radiation of a wavelength of 248 to 436nm. A suitable exposure dose is 10 to 10,000mJ / cm 2 .

[0144] Exposure can be accomplished by a photomask. The photomask used herein can be, for example, the kind that passes through with a desired pattern. Although the material of the photomask is not particularly limited, it is preferably a material that can shield radiation within the above-mentioned wavelength range. For example, a mask with a chromium light-shielding film is preferred.

[0145] The next step may be post-exposure baking (PEB), which is effective for enhancing the developing photosensitivity. PEB is performed, for example, at 40 to 150° C. for 0.5 to 10 minutes. PEB induces crosslinking in the exposed areas of the resin film, forming an insoluble pattern that is insoluble in a developer or an organic solvent.

[0146] Step (iii) after exposure or PEB is to develop the exposed resin film with a developer to form a pattern. Preferred developers are organic solvents, such as alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether (PGME). Solvents used in photosensitive resin compositions can also be used for development. Development is carried out in a conventional manner, for example, by immersing the exposed film in a developer. By developing in an organic solvent-based developer, the unexposed areas of the resin film are dissolved to generate a pattern. If necessary, development is followed by washing, rinsing and drying. In this way, a resin film with a desired pattern is obtained.

[0147] In step (iv), the patterned film can be post-cured in an oven or hot plate at a temperature preferably of 100 to 250° C., more preferably 150 to 220° C. Using the photosensitive resin composition of the present invention now, a resin film having excellent film properties can be obtained, even from post-curing at a relatively low temperature of about 200° C. A post-curing temperature of 100 to 250° C. is preferred from the viewpoint of substrate adhesion, heat resistance, strength, electrical properties and bonding strength, because this temperature range is effective for increasing the cross-linking density of the resin film and removing any residual volatile substances. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. After post-curing, the resin film typically has a thickness of 1 to 200 μm, preferably 5 to 50 μm. Through these steps, a desired anti-reflection film can be obtained.

[0148] Example

[0149] Examples of the present invention are given below by way of illustration and not by way of limitation. It is noted that the weight average molecular weight (Mw) is measured relative to a monodisperse polystyrene standard by GPC under conditions including a TSKgel Super HZM-H (Tosoh Corp.) column, a flow rate of 0.6 mL / min, an eluent of THF, and a column temperature of 40° C. All parts are by weight (pbw).

[0150] Compounds (S-1) to (S-5) used in Examples and Comparative Examples are embodied as follows.

[0151]

[0152] [1] Synthesis of silicone resins containing acid-crosslinkable groups

[0153] Synthesis Example 1

[0154] Synthesis of Resin A-1

[0155] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 265.0 g (1.00 mol) of compound (S-5), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 164.9 g (0.85 mol) of compound (S-1) and 453.0 g (0.15 mol) of compound (S-2) (y 1 =40, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, in molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-1. 1 H-NMR and 29 The structure of Resin A-1 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-1 had an Mw of 65,000 and a silicone content of 51.3 wt%.

[0156] Synthesis Example 2

[0157] Synthesis of Resin A-2

[0158] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 111.6 g (0.60 mol) of compound (S-3) and 156.8 g (0.40 mol) of compound (S-4), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 135.8 g (0.70 mol) of compound (S-1) and 906.0 g (0.30 mol) of compound (S-2) (y were added dropwise over 1 hour. 1 =40, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, by molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-2. 1 H-NMR and 29 The structure of Resin A-2 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-2 had an Mw of 55,000 and a silicone content of 77.7 wt%.

[0159] Synthesis Example 3

[0160] Synthesis of Resin A-3

[0161] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 111.6 g (0.60 mol) of compound (S-3) and 106.0 g (0.40 mol) of compound (S-5), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2) (y were added dropwise over 1 hour. 1 =40, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, by molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-3. 1 H-NMR and 29 The structure of Resin A-3 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-3 had an Mw of 50,000 and a silicone content of 59.6 wt%.

[0162] Synthesis Example 4

[0163] Synthesis of Resin A-4

[0164] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 392.0 g (1.00 mol) of compound (S-4), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 155.2 g (0.80 mol) of compound (S-1) and 317.0 g (0.20 mol) of compound (S-2) (y were added dropwise over 1 hour. 1 = 20, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, by molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-4. 1 H-NMR and 29 The structure of Resin A-4 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-4 had an Mw of 23,000 and a silicone content of 36.7 wt%.

[0165] Synthesis Example 5

[0166] Synthesis of Resin A-5

[0167] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 274.4 g (0.70 mol) of compound (S-4) and 79.5 g (0.30 mol) of compound (S-5), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 58.2 g (0.30 mol) of compound (S-1) and 1109.5 g (0.70 mol) of compound (S-2) (y were added dropwise over 1 hour. 1 = 20, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-5. 1 H-NMR and 29 The structure of Resin A-5 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-5 had an Mw of 42,000 and a silicone content of 72.9 wt%.

[0168] Synthesis Example 6

[0169] Synthesis of Resin A-6

[0170] A 3L flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 55.8 g (0.30 mol) of compound (S-3), 117.6 g (0.30 mol) of compound (S-4) and 106.0 g (0.40 mol) of compound (S-5), and then charged with 2,000 g of toluene and heated at 70° C. Thereafter, 1.0 g of a chloroplatinic acid toluene solution (Pt concentration 0.5 wt%) was added, and 135.8 g (0.70 mol) of compound (S-1) and 475.5 g (0.30 mol) of compound (S-2) (y were added dropwise over 1 hour. 1 = 20, Shin-Etsu Chemical Co., Ltd.) (total hydrosilyl group / total alkenyl group = 1 / 1, in molar ratio). After the dropwise addition was completed, the reaction solution was heated at 100° C. and aged for 6 hours. Toluene was distilled off from the reaction solution in a vacuum to produce resin A-6. 1 H-NMR and 29 The structure of Resin A-6 was analyzed by Si-NMR spectroscopy (Bruker Corp.) and GPC. Resin A-6 had a Mw of 31,000 and a silicone content of 59.6 wt%.

[0171] Comparative Synthesis Example 1

[0172] Synthesis of acrylic resin 1

[0173] A flask equipped with a stirrer, a thermometer, a nitrogen purge line and a reflux condenser was charged with 70 g of PGME and 70 g of toluene. The flask was heated at 80 ° C under a nitrogen atmosphere. While the reaction temperature was maintained at 80 ± 2 ° C, 90 g of methyl methacrylate, 10 g of methacrylic acid and 2,2'-azobis(isobutyronitrile) were continuously added dropwise for 4 hours. After the addition, stirring was continued at 80 ± 2 ° C for 6 hours to generate a solution of acrylic resin 1. Acrylic resin 1 has an Mw of 50,000.

[0174] [2] Preparation and evaluation of photosensitive resin compositions

[0175] Examples 1 to 14 and Comparative Examples 1 to 18

[0176] The photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 18 were prepared by combining the respective components according to the formulations shown in Tables 1 to 4, stirring, mixing and dissolving at room temperature.

[0177] Table 1

[0178]

[0179]

[0180] Table 2

[0181]

[0182] Table 3

[0183]

[0184] Table 4

[0185]

[0186] In Tables 1 to 4, hollow silica C-1 is TMPS-1.5 (average particle size 8.8 μm) of Taiyo Kagaku Co., Ltd. and hollow silica C-2 is Thrulya 4320 (average particle size 60 μm) of JGC C&C. Tetraethoxysilane and (3,3,3-trifluoropropyl)triethoxysilane are available from Shin-Etsu Chemical Co., Ltd. Photoacid generator B-1, crosslinking agents D-1 to D-3, antioxidants E-1 and E-2, acrylic resin 2 and Irgacure OXE02 are embodied as follows.

[0187] Photoacid generator B-1

[0188]

[0189] Crosslinking agent D-1 (Shin-Etsu Chemical Co., Ltd.)

[0190]

[0191] Crosslinking agent D-2 (Shikoku Chemicals Corp.)

[0192]

[0193] Crosslinking agent D-3 (Shikoku Chemicals Corp.)

[0194]

[0195] Antioxidant E-1: Chimassorb 119FL (BASF)

[0196]

[0197] Antioxidant E-2: Irganox 3114 (BASF)

[0198]

[0199] Acrylic resin 2: DPCA-20, Nippon Kayaku Co., Ltd. (ε-caprolactone-modified dipentaerythritol acrylate of the following formula)

[0200]

[0201] Irgacure OXE02: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), manufactured by BASF

[0202] [3] Evaluation of resin films

[0203] (1) Pattern formation and evaluation

[0204] Using a spin coater, each photosensitive resin composition is coated on a glass substrate to form a 3 μm thick film. The coated substrate is placed on a hot plate and heated and dried at 110 ° C for 3 minutes to evaporate the solvent from the composition. Using a contact aligner type exposure system, the photosensitive resin film is exposed to 365nm radiation by a mask suitable for forming a line-space pattern and a contact hole pattern. The resin film is exposed to post-baking (PEB) for 3 minutes at 120 ° C on a hot plate and then cooled. The resin film is developed by spraying PGMEA for 60 seconds to form a pattern.

[0205] The photosensitive resin film on the substrate patterned as above was post-cured in an oven where the film was heated at 190°C for 2 hours while the oven was purged with nitrogen. The resulting contact hole patterns of 50 μm, 30 μm, 20 μm and 10 μm were observed in cross section under a scanning electron microscope (SEM). The smallest hole pattern in which the hole passed through the film to the bottom was recorded as the maximum resolution. When a pattern could not be formed, the resin film was rated as "NG" in terms of resolution.

[0206] (2) Evaluation of reliability (adhesion and crack resistance)

[0207] The substrate with the photosensitive resin film (of Examples 1 to 14 and Comparative Examples 1 to 18) patterned and post-cured in (1) was cut into 10 mm×10 mm square pieces (test samples) by running a dicing saw (DAD685 of DISCO Corp.) with a dicing blade at a shaft speed of 40,000 rpm and a cutting rate of 20 mm / sec. Ten test samples (for each example) were subjected to a thermal cycle test of 1,000 cycles of repeated maintenance at -25°C for 10 minutes and at 125°C for 10 minutes. After the thermal cycle test, it was observed whether the resin film peeled off from the substrate and whether the resin film cracked. When no sample peeled off or cracked, these samples were rated as "OK", when one or more samples peeled off, these samples were rated as "with peeling", and when one or more samples cracked, these samples were rated as "with cracking".

[0208] (3) Flexibility test

[0209] The resin film prepared as above was wound on a shaft of 5 mm in diameter, kept still for 10 seconds, and unwound. The film was checked for any abnormality after the winding / unwinding operation was repeated 10 times. The film was rated as "OK" when there was no change, and rated as "NG" when cracks or splits were found.

[0210] (4) Light reflectance measurement test

[0211] The film sample was rubbed several times with sandpaper on its back side and painted with matte black paint. The reflectivity on the front side was measured by using a spectrophotometer U-3310 (Hitachi High-Tech Science Corp.) and directing light of wavelength 400-700 nm at an incident angle of 5°. The minimum reflectivity (%) within the measurement range was recorded as the light reflectivity.

[0212] (5) Light transmission test 1

[0213] Using a spin coater, each photosensitive resin composition was applied onto an 8-inch glass wafer to form a 3 μm thick resin film. The coated wafer was placed on a hot plate and heated and dried at 100° C. for 5 minutes to remove the solvent from the composition.

[0214] The film on the glass wafer was exposed to light of 360 nm wavelength directly (i.e., without passing through a mask) from a high pressure mercury lamp (full exposure) with its entire surface using Mask Aligner MA8 (SUSS MicroTec AG). The film was subjected to PEB and entered into PGMEA. The film left after these operations was then heated in an oven at 190° C. for 2 hours to produce a cured film. The transmittance of light of 450 nm wavelength of the cured film was measured using a spectrophotometer U-3900H (Hitachi High-Tech Science Corp.).

[0215] (6) Light transmission test 2

[0216] The sample in the form of a resin film on a glass wafer prepared as above was continuously exposed to laser radiation of a wavelength of 450 nm and a power of 1 W in an oven at 140° C. After a lapse of 1,000 hours, the transmittance of light of a wavelength of 450 nm was measured.

[0217] The results are shown in Tables 5 to 7.

[0218] Table 5

[0219]

[0220] Table 6

[0221]

[0222]

[0223] Table 7

[0224]

[0225] As confirmed by the test results, the photosensitive resin composition within the scope of the present invention is easy to form an anti-reflection film. The cured film of the photosensitive resin composition of the present invention acts as an anti-reflection film and has light resistance, excellent micro-processing performance factors such as resolution, satisfactory reliability (adhesion, crack resistance) and flexibility.

[0226] Japanese Patent Application No. 2018-216419 is incorporated herein by reference.

[0227] While some preferred embodiments have been described, many modifications and variations are possible in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

Claims

1. A photosensitive resin composition comprising: (A) an organosilicon resin containing acid-crosslinkable groups, (B) a photoacid generator, and (C) hollow silica, wherein the acid crosslinkable group is an epoxy group, Component (A) is a silicone resin composed of repeating units having the following formulae (A1) to (A6): in, R 1 To R 4 Each independently is a C1-C 20 monovalent hydrocarbon group, m independently being an integer from 1 to 600, provided that when m is an integer of at least 2, the group R 3 Optionally the same or different and group R 4 are optionally the same or different, a, b, c, d, e and f are numbers in the following ranges: 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0 ≤ d ≤ 1, 0 ≤ e≤ 1, 0 ≤ f ≤ 1, 0 < c+d+e+f ≤ 1 and a+b+c+d+e+f=1, X 1 is a divalent group having the formula (X1): Among them, R 11 To R 14 Each independently is a C1-C 20 a monovalent hydrocarbon radical, p being an integer from 1 to 600, provided that when p is an integer of at least 2, the radical R 13 Optionally the same or different and group R 14 Optional same or different, R 15 and R 16 are each independently hydrogen or methyl, and x is each independently an integer from 0 to 7, X 2 is a divalent group having the formula (X2): Among them, Y 1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group, R 21 and R 22 are each independently C1-C4 alkyl or alkoxy, provided that when g is 2, the group R 21 Optional the same or different, when h is 2, the group R 22 Optional same or different, R 23 and R 24 are each independently hydrogen or methyl, y are each independently an integer from 0 to 7, g and h are each independently 0, 1 or 2, X 3 is a divalent group having the formula (X3): Among them, R 31 and R 32 are each independently hydrogen or methyl, z is each independently an integer from 0 to 7, R 33 is a C1-C8 monovalent hydrocarbon group optionally containing an ester bond or an ether bond, or a monovalent group having the formula (X3-1): Among them, R 34 It is a C1-C8 divalent hydrocarbon group which may contain an ester bond or an ether bond. 2 . The photosensitive resin composition according to claim 1 , wherein the hollow silica (C) has an average particle size of at most 1 μm. 3 . The photosensitive resin composition according to claim 1 , wherein the hollow silica (C) is present in an amount of 20 to 90 wt % of the composition. The photosensitive resin composition according to claim 1 , further comprising (D) a crosslinking agent. The photosensitive resin composition according to claim 1 , further comprising (E) an antioxidant. The photosensitive resin composition according to claim 1 , further comprising (F) a solvent. 7 . The photosensitive resin composition according to claim 1 , wherein the weight average molecular weight of the silicone resin containing an acid-crosslinkable group is 3,000 to 500,000.

8. A pattern forming method comprising the following steps: (i) applying the photosensitive resin composition according to claim 1 onto a substrate to form a photosensitive resin film thereon, (ii) exposing the photosensitive resin film to radiation, and (iii) The exposed resin film is developed in a developer.

9. A method for preparing an anti-reflection film, comprising the pattern forming method according to claim 8, wherein the anti-reflection film comprises a patterned photosensitive resin film. 10 . An anti-reflection film comprising the photosensitive resin composition according to claim 1 .

11. An article comprising the anti-reflection film according to claim 10.

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