Polymerizable composition, adhesive, sealing material, cured product, semiconductor device, and electronic component

Abstract

The present invention addresses the problem of providing at least a photocurable or thermosetting polymerizable composition and adhesive capable of suppressing a bleeding phenomenon.　Provided are a polymerizable composition and an adhesive that contain (A) a cationically polymerizable compound, (B) an acid generator, and (C) a modified polydimethylsiloxane that satisfies at least one of the following features (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; and (c) the modified polydimethylsiloxane has a specific signal in a 1H NMR spectrum measured in deuterated chloroform and satisfies a specific formula.

Description

Polymerizable compositions, adhesives, sealing materials, cured products, semiconductor devices, and electronic components

[0001] The present invention relates to a polymerizable composition, an adhesive or sealing material containing the same, a cured product thereof, and a semiconductor device and an electronic component containing the cured product.

[0002] BACKGROUND ART At present, adhesives, sealants, etc. containing curable resin compositions are often used for the assembly and mounting of components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability.

[0003] Development of photocurable and / or low-temperature curable resin compositions has been progressing. For example, Patent Documents 1 and 2 disclose photocurable and low-temperature curable cationically curable resin compositions.

[0004] Republished Patent Publication No. 2017 / 094584 Japanese Patent Application Laid-Open No. 2021-147584

[0005] Bleeding is an issue in the assembly process of semiconductor modules. Bleeding is a phenomenon in which unreacted components seep out from the adhesive coating or cured product over time when an adhesive containing a curable resin composition is used to fix or bond components. The exuded components themselves are sometimes referred to as "bleed." When the bleed comes into contact with metal wiring on the substrate, it can cause electrical defects, resulting in reduced reliability of the semiconductor module. In particular, inner bleed, which occurs from uncured portions of the adhesive, tends to progress when the adhesive coating is left at room temperature and / or during thermal curing, and the bleed length tends to increase.

[0006] In recent years, there has been a growing demand for smaller and more highly integrated electronic components such as semiconductor chips, and the distance to the wiring parts arranged around the electronic components is becoming shorter. In semiconductor modules equipped with such smaller and more highly integrated electronic components, there is a problem that the bleeding phenomenon increases the risk of contact between the bleeding and the wiring parts.

[0007] Therefore, an object of the present invention is to provide at least a photocurable or thermosetting polymerizable composition and adhesive that can suppress the bleeding phenomenon.

[0008] Specific means for solving the above problems are as follows. Aspects of the present invention include the following polymerizable compositions, adhesives or sealants, cured products, and semiconductor devices or electronic components. [1] (A) a cationically polymerizable compound, (B) an acid generator, and (C) a modified polydimethylsiloxane satisfying at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) a cationically polymerizable compound (A) having an acid generator (B) an acid generator (C) a modified polydimethylsiloxane satisfying at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) a cationically polymerizable compound (B) having an acid generator (C) a modified polydimethylsiloxane satisfying at least one of the following characteristics (a), (b), and (c) １ In the H NMR spectrum, there are signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, there are signals or no signals in the range of 1.25 to 0.95 ppm, and there are signals in the range of 13 to 0 ppm. ２A polymerizable composition having a signal that disappears upon addition of O, and a value calculated by the following formula (1) of less than 0.3: Formula (1): [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4}. [2] The polymerizable composition according to the above item [1], wherein the (A) cationically polymerizable compound comprises a compound having an epoxy group and a compound having an oxetanyl group. [3] The polymerizable composition according to the above item [1] or [2], wherein the content of the (C) modified polydimethylsiloxane is 0.01 to 5 mass % relative to the total mass of the polymerizable composition. [4] The polymerizable composition according to any one of the above items [1] to [3], further comprising (D) a filler. [5] The polymerizable composition according to any one of [1] to [4] above, wherein components (A) to (C) are contained in a single container. [6] The polymerizable composition according to any one of [1] to [4] above, wherein components (A) to (C) are separated into two or more containers. [7] An adhesive or sealant comprising the polymerizable composition according to any one of [1] to [6] above. [8] The adhesive or sealant according to [7] above, which is used for fixing, adhering, or protecting an optical sensor module or a component constituting the same. [9] A cured product obtained by curing the polymerizable composition according to any one of [1] to [6] above, or the adhesive or sealant according to [7] or [8] above.

[10] A semiconductor device or electronic component comprising the cured product according to [9] above.

[11] The semiconductor device or electronic component according to

[10] above, which is an optical sensor module.

[0009] According to aspects of the present invention, there are provided at least a photocurable or thermosetting polymerizable composition capable of suppressing the bleeding phenomenon, an adhesive or sealant containing the same, a cured product obtained by curing the composition or the sealant, and a semiconductor device or electronic component containing the cured product.

[0010] [Polymerizable Composition] The polymerizable composition according to one embodiment of the present invention comprises: (A) a cationically polymerizable compound; (B) an acid generator; and (C) a modified polydimethylsiloxane that satisfies at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and, optionally, an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) a cationically polymerizable compound (A) is a cationically polymerizable compound; (B) an acid generator (C) is a modified polydimethylsiloxane that satisfies the following characteristics (a), (b), and (c) １ In H NMR, there are signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, there are signals or no signals in the range of 1.25 to 0.95 ppm, and there are signals in the range of 13 to 0 ppm. ２ The polymerizable composition has a signal that disappears upon addition of O, and the value calculated by the following formula (1) is less than 0.3: Formula (1): [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4}. According to this aspect, it is possible to provide a polymerizable composition that is at least photocurable or thermosetting and that can suppress the bleeding phenomenon.

[0011] (A) Cationic Polymerizable Compound The polymerizable composition of this embodiment contains (A) a cationic polymerizable compound (hereinafter also referred to as "component (A)"). Examples of the (A) cationic polymerizable compound include, but are not limited to, compounds having an epoxy group, compounds having an oxetanyl group, compounds having a vinyl ether group, compounds having other cationic polymerizable groups, and compounds having any combination of these cationic polymerizable groups. In one embodiment, the cationic polymerizable compound preferably contains a compound having an epoxy group and a compound having an oxetanyl group.

[0012] In this specification, a compound having an epoxy group refers to a compound having at least one epoxy group in the molecule, and is also referred to as an epoxy compound. Examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In this embodiment, the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds depending on the type of skeleton.

[0013] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in the molecule, and is also referred to as an oxetane compound. In an embodiment, the oxetane compound preferably has 1 to 6 oxetanyl groups in the molecule, and more preferably has 1 to 2 oxetanyl groups in the molecule.

[0014] In this specification, a compound having a vinyl ether group is a compound having at least one vinyl ether group in the molecule.

[0015] Specific examples of the cationic polymerizable compound include glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-eth ... 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propanediol Pan-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized polybutadiene, compounds in which some or all of the double bonds of styrene-butadiene copolymers have been epoxidized, bis[1-ethyl(3-oxetanyl)]methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl) oxetane), xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3- Examples of the vinyl ether include, but are not limited to, (4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, oxetanylsilsesquioxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, phenol novolac oxetane, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, 1,4-cyclohexanedimethanol monovinyl ether, and 1,4-cyclohexanedimethanol divinyl ether.

[0016] Commercially available cationically polymerizable compounds include EPICLON (registered trademark) 850, 850-S, EXA-850CRP, and EXA-8067 manufactured by DIC Corporation; AER9000 manufactured by Asahi Kasei Corporation; EP-4000S, EP-4003S, and EP-4010S manufactured by ADEKA Corporation; EPICLON (registered trademark) 830-S, EXA-830LVP, and EXA-835LV manufactured by DIC Corporation; and EPICLON (registered trademark) HP-40 manufactured by DIC Corporation. 32D, HP-720H; EPICLON (registered trademark) N-740, N-770 manufactured by DIC Corporation; EPICLON (registered trademark) N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; ADEKA GLYCIROL (registered trademark) ED-509E, ED-509S manufactured by ADEKA Corporation; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; AER-9000 manufactured by Asahi Kasei Corporation; jER manufactured by Mitsubishi Chemical Corporation YX7400N; jER YX8000 manufactured by Mitsubishi Chemical Corporation; CELLOXIDE (registered trademark) 2021P manufactured by Daicel Corporation; CELLOXIDE (registered trademark) 8010 manufactured by Daicel Corporation; EHPE3150 manufactured by Daicel Corporation; EPOLEAD PB manufactured by Daicel Corporation; EPOFRIEND manufactured by Daicel Corporation; HiREM-1 and HiREM-2 manufactured by Shikoku Chemicals Corporation; OXT-191 manufactured by Toagosei Co., Ltd.; OXT-221 manufactured by Toagosei Co., Ltd.; PHOX manufactured by Toagosei Co., Ltd., and the like, but are not limited to these.

[0017] The cationically polymerizable compounds may be used alone or in combination of two or more.

[0018] The cationically polymerizable group equivalent of the cationically polymerizable compound is preferably 90 to 1000 g / eq, more preferably 120 to 800 g / eq, and even more preferably 150 to 500 g / eq.

[0019] From the viewpoint of preparation and dispensability of the polymerizable composition, it is preferable that component (A) has a viscosity of 0.001 to 100 Pa s. In this specification, viscosity refers to a value measured at a measurement temperature of 25°C using a viscometer appropriate for the viscosity range.

[0020] From the viewpoint of adhesive strength of the polymerizable composition, the content of component (A) is preferably 10 to 95 mass %, more preferably 20 to 90 mass %, based on the total mass of the polymerizable composition.

[0021] (B) Acid Generator The polymerizable composition of this embodiment contains (B) an acid generator (hereinafter also referred to as "component (B)"). In this specification, the acid generator generates an acid as an active species by light or heat, and promotes the polymerization of the cationically polymerizable compound. Examples of the acid generator include BF ４ － , SbF ６ -, AsF ６ － , B(C ６ F ５ ) ４ － , Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , [P(R １ ) ａ F ６－ａ ] － , [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R １ may be the same or different.) as a counter anion, and an iodonium cation, a sulfonium cation, an ammonium cation, a phosphonium cation, or the like as a cation moiety.

[0022] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0023] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio] phenyl} sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium,10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium triarylsulfoniums such as 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium and 5-(2,4,6-trimethylphenyl)thiaanthrenenium; diarylsulfonium such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium and diphenylmethylsulfonium; monoarylsulfonium such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium and 9-anthracenylmethylphenacylsulfonium; Examples include trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

[0024] Examples of ammonium cations include pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; and morpholiniums such as N,N'-dimethylmorpholinium. pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazolium such as N,N'-dimethylimidazolium; quinolium such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.

[0025] Examples of the phosphonium cation include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0026] Specific examples of the iodonium salt-based acid generator include photoacid generators that are arsenate-based iodonium salts such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF), and bis(C １０～１４ photoacid generators which are phosphate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate (e.g., WPI-113 manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (here, IK-1 manufactured by San-Apro Co., Ltd. can also be used as a thermal acid generator); photoacid generators which are antimonate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (e.g., WPI-116 manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.); photoacid generators which are gallate-based iodonium salts such as IK-1FG (manufactured by San-Apro Co., Ltd.) (here, IK-1FG can also be used as a thermal acid generator); Photoacid generators which are borate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (e.g., BLUESIL (registered trademark) PI 2074 manufactured by ELKEM SILICONES), but are not limited to these.

[0027] Specific examples of sulfonium salt-based acid generators include, but are not limited to, photoacid generators which are borate-based sulfonium salts (products manufactured by San-Apro Ltd. under the trade names CPI-110B, CPI-310B, CPI-410B, etc.), photoacid generators which are phosphate-based sulfonium salts (products manufactured by San-Apro Ltd. under the trade names CPI-210S, VC-1S, CPI-410S, etc.), thermal acid generators which are phosphate-based sulfonium salts (products manufactured by San-Apro Ltd. under the trade name TA-100, etc.), photoacid generators which are gallate-based sulfonium salts (products manufactured by San-Apro Ltd. under the trade names CPI-310FG, VC-1FG, etc.), and thermal acid generators which are gallate-based sulfonium salts (products manufactured by San-Apro Ltd. under the trade name TA-100FG, etc.).

[0028] Specific examples of ammonium hydrochloric acid generators include, but are not limited to, thermal acid generators that are borate-based quaternary ammonium salts (product name: CXC-1821, manufactured by King Industries, Inc.).

[0029] In this embodiment, the content of the acid generator (B) in the polymerizable composition is preferably 0.1 to 10 mass %, more preferably 0.3 to 8 mass %, and even more preferably 0.5 to 5 mass %, relative to the total mass of the polymerizable composition. The content of the acid generator (B) in the polymerizable composition is preferably 0.1 to 30 mass %, more preferably 0.5 to 20 mass %, and even more preferably 1 to 15 mass %, relative to the total mass of the component (A).

[0030] (C) Modified Polydimethylsiloxane The polymerizable composition of this embodiment contains (C) modified polydimethylsiloxane (hereinafter also referred to as "component (C)"). In this embodiment, the (C) modified polydimethylsiloxane satisfies at least one of the following characteristics (a), (b), and (c): (a) An organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker. (b) An organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3. (c) The solubility measured in deuterated chloroform １ In the H NMR spectrum, there are signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, there are signals or no signals in the range of 1.25 to 0.95 ppm, and there are signals in the range of 13 to 0 ppm. ２ The sample has a signal that disappears upon addition of O, and the value calculated from the following formula (1) is less than 0.3: [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4}

[0031] More specifically, the modified polydimethylsiloxane is represented by the formula: The polydimethylsiloxane has a structure in which organic substituents have been introduced as modifying groups into the side chains and / or terminals of the polydimethylsiloxane main chain, which is composed of dimethylsiloxane repeating units represented by the formula: directly or via a linker such as an alkyl group or an alkylene group. Here, "an organic substituent has been introduced into the side chain of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. "an organic substituent has been introduced into the terminal of the polydimethylsiloxane main chain" means that some of the methyl groups in the polydimethylsiloxane main chain have been substituted with organic substituents. ３ ) ３) is substituted with an organic substituent. The position of the modifying group in the modified polydimethylsiloxane may be a side chain, a terminal (one terminal or both terminals), or both a side chain and a terminal. Modified polydimethylsiloxanes also include polydimethylsiloxanes with a gemini structure. The degree of polymerization of the modified polydimethylsiloxane (the number of dimethylsiloxane repeating units) is not particularly limited and is, for example, 3 or more, preferably 5 or more.

[0032] In the modified polydimethylsiloxane according to the above feature (a), the organic substituent contains a COOH group.

[0033] Examples of modified polydimethylsiloxanes in which the organic substituent contains a COOH group include those commercially available under the names of carboxyl-modified polydimethylsiloxanes or carboxyl-modified silicones, etc. Examples of such commercially available products include, but are not limited to, product names X-22-3701E, X-22-162C, and X-22-3710 sold by Shin-Etsu Chemical Co., Ltd.

[0034] Whether the organic substituent of the modified polydimethylsiloxane contains a COOH group can be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and determining whether the COOH group is present at approximately 1715 cm , which is derived from the C═O stretching vibration of carboxylic acid. －１ This can also be done by observing the presence or absence of IR spectrum of

[0035] In the modified polydimethylsiloxane according to the above feature (b), the organic substituent contains an OH group and optionally an ether group, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol (PPG) repeating units to the number of polyethylene glycol (PEG) repeating units in the organic substituent is less than 0.3. In feature (b), examples of ether groups that may be optionally contained in the organic substituent include polyethylene glycol groups and polypropylene glycol groups. In feature (b), when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units is preferably less than 0.1, and more preferably less than 0.01 (i.e., the organic substituent is substantially free of polypropylene glycol repeating units). In one embodiment, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units may be 0.

[0036] Examples of modified polydimethylsiloxanes in which the organic substituent contains an OH group but does not contain an ether group include those commercially available as carbinol-modified polydimethylsiloxanes or carbinol-modified silicones, etc. Examples of commercially available products of such compounds include, but are not limited to, product names X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, and X-22-170DX sold by Shin-Etsu Chemical Co., Ltd.

[0037] Examples of modified polydimethylsiloxanes in which the organic substituents contain OH groups and ether groups include those called polyether-modified polydimethylsiloxanes or polyether-modified silicones, in which the polyether groups terminate with OH groups. Examples of commercially available products of this type in which the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units is less than 0.3 include, but are not limited to, product names X-22-4272 and KF-6123 sold by Shin-Etsu Chemical Co., Ltd. Furthermore, such polyether-modified polydimethylsiloxanes or polyether-modified silicones are sometimes labeled "PEG-(number) dimethicone" in cosmetic product names. "PEG-(number)" indicates that the average number of PEG (polyethylene glycol) chains is the corresponding number. "PEG-(number) dimethicone" is abbreviated as "PEG-(n) DIMETHICONE" in the INCI nomenclature. Examples of such dimethicones in which the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units is less than 0.3 include, but are not limited to, PEG-9 dimethicone (product name: KF-6013), PEG-3 dimethicone (sold by Shin-Etsu Chemical Co., Ltd., product name: KF-6015), PEG-10 dimethicone (sold by Shin-Etsu Chemical Co., Ltd., product name: KF-6017), PEG-10 dimethicone (sold by Shin-Etsu Chemical Co., Ltd., product name: KF-6043), and the like.

[0038] Reactive silicones whose hydroxyl value is disclosed in a catalog or the like can also be assumed to be modified polydimethylsiloxanes in which the organic substituents contain OH groups and, optionally, ether groups. The hydroxyl value of the modified polydimethylsiloxane may be measured to confirm the presence of OH groups in the modified polydimethylsiloxane. In one embodiment, the modified polydimethylsiloxane has a hydroxyl value of 1 mg KOH / g or more. The hydroxyl value can be measured, for example, by a method conforming to JIS K 0070 or by FT-NIR (near-infrared spectroscopy) conforming to JIS K 1557-6. Whether the organic substituents of the modified polydimethylsiloxane contain OH groups can be confirmed by measuring the hydroxyl value of the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and detecting a hydroxyl value of approximately 1360 to 1340 cm resulting from the deformation vibration of alcoholic OH. －１ This can also be done by observing the presence or absence of IR spectrum of

[0039] When the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent can be determined from the structure of the modified polydimethylsiloxane disclosed in a catalog or the like. For example, when it is clear that the modified polydimethylsiloxane contains OH groups and ether groups but does not contain polypropylene glycol repeating units, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units will be 0, satisfying feature (b). When a specific structure is not disclosed, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units can be determined by measuring the modified polydimethylsiloxane in deuterated chloroform, as described below with respect to feature (c). １ It can be calculated based on the H NMR spectrum. Specifically, it can be calculated based on the H NMR spectrum of the modified polydimethylsiloxane measured in deuterated chloroform. １Based on the H NMR spectrum, the value calculated by the following formula (1) can be regarded as the ratio of the number of repeating units of polypropylene glycol to the number of repeating units of polyethylene glycol: Formula (1): [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4}

[0040] In some commercially available modified polydimethylsiloxanes, the detailed structure of the modifying group is not disclosed. Furthermore, there are also various commercially available additives such as surfactants, surface conditioners, leveling agents, antifoaming agents, wetting agents, and dispersants, which are considered modified polydimethylsiloxanes even though they are not explicitly labeled as modified polydimethylsiloxanes or their structure is not disclosed. In such cases, the modified polydimethylsiloxane was measured in deuterated chloroform. １ In the H NMR spectrum, there are signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, there are signals or no signals in the range of 1.25 to 0.95 ppm, and there are signals in the range of 13 to 0 ppm. ２ The modified polydimethylsiloxane of this embodiment has a signal that disappears upon addition of O, and the value calculated by the following formula (1) is less than 0.3 (the above-mentioned feature (c)). Formula (1): [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4} The signal observed in the range of 0.3 to -0.3 ppm (hereinafter also referred to as "first signal") is a hydrogen atom (-Si(CH)) attached to a carbon atom adjacent to a Si atom. ３ ) ２ The signal observed in the range of 4.4 to 3.2 ppm (hereinafter also referred to as the "second signal") is a signal derived from a hydrogen atom (for example, -O-CH) connected to a carbon atom adjacent to an OH group or an oxygen atom of an ether. ２ CH ２ —O—, —O—CH ２ CH (CH ３ ) —O—, —CH ２The signal observed in the range of 1.25 to 0.95 ppm (hereinafter also referred to as the "third signal") is a signal derived from a hydrogen atom (-CH) of a methyl group in a polypropylene glycol chain as a polyether modifying group. ２ CH (CH ３ )-O-) signals are observed in the range of 13 to 0 ppm, and D ２ The signal that disappears upon addition of O (hereinafter also referred to as the "fourth signal") can be presumed to be a signal derived from the hydrogen atom of an OH group or an NH group.

[0041] D ２ The signal that disappears upon addition of O is usually observed in the range of 13 to 0 ppm. Among them, the signal that disappears in the range of 3 to 2 ppm and D ２ The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group.

[0042] D ２ It can be estimated whether the signal that disappears upon addition of O is a signal derived from a hydrogen atom of an OH group or an NH group, for example, by the following method: Fourier transform infrared spectroscopy (FT-IR) measurement １ In addition to the H NMR measurement, Fourier transform infrared spectroscopy (FT-IR) measurement of the modified polydimethylsiloxane revealed a peak at approximately 1360 to 1340 cm , which is due to the deformation vibration of alcoholic OH. －１ By observing the presence or absence of IR spectrum of D ２ The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group. １ In addition to the H NMR measurement, the acidity of the modified polydimethylsiloxane was measured. ２ The signal that disappears upon addition of O can be estimated as being derived from either the OH group or the NH group hydrogen atom. For example, 100 mg of a measurement sample of modified polydimethylsiloxane is dissolved in 200 uL of isopropyl alcohol, 200 uL of pure water is added, and the mixture is shaken well, and the pH of the liquid is measured. If the pH is between 3 and 7, D ２The signal that disappears upon addition of O can be assumed to be a signal derived from the hydrogen atom of the OH group. ２ The signal that disappears upon addition of O can be presumed to be a signal derived from the hydrogen atom of the NH group.

[0043] In the above feature (c), the value calculated from formula (1) is less than 0.3. Here, this value roughly corresponds to the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the modified polydimethylsiloxane, as shown below. In formula (1), the signal (first signal) observed in the range of 0.3 to -0.3 ppm is the dimethylsiloxane repeating unit -O-Si(CH ３ ) ２ The signal (second signal) observed in the range of 4.4 to 3.2 ppm is attributed to the underlined hydrogen atom of -, and is a polyethylene glycol repeating unit -O-CH ２ CH ２ The underlined hydrogen atom of —O— and the polypropylene glycol repeating unit —O—CH ２ CH (CH ３ The signal observed in the range of 1.25 to 0.95 ppm (third signal) is attributed to the underlined hydrogen atom of the -O- polypropylene glycol repeating unit -CH ２ CH (CH ３)-O-. Under the above assumptions, when the integral of each signal is calculated assuming that the integral of the first signal corresponding to one dimethylsiloxane repeating unit is 6, the number of polypropylene glycol repeating units per dimethylsiloxane repeating unit can be calculated using the following formula (2): Formula (2): (integral of the third signal) / 3 Similarly, the number of polyethylene glycol repeating units per dimethylsiloxane repeating unit can be calculated using the following formula (3): Formula (3): [(integral of the second signal) - (integral of the third signal)] / 4 Based on the above formulas (2) and (3), the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the modified polydimethylsiloxane can be calculated using formula (1): Formula (1): [(integral of the third signal) / 3] / {[(integral of the second signal) - (integral of the third signal)] / 4}

[0044] Examples of modified polydimethylsiloxanes that satisfy characteristic (c) include those sold by Shin-Etsu Chemical Co., Ltd. under the product names KF-945 and X-22-4039, and those sold by Evonik Japan Co., Ltd. under the product names TEGO TWIN 4000 and TEGO TWIN 4100.

[0045] In the polymerizable composition of this embodiment, the inclusion of (C) a modified polydimethylsiloxane satisfying at least one of characteristics (a), (b), and (c) suppresses bleeding after application to a substrate or the like, not only during thermal curing but also when left at room temperature. The reason why the inclusion of (C) a modified polydimethylsiloxane in the polymerizable composition suppresses bleeding is thought to be, but is not limited to, the following: When a polymerizable composition containing a modified polydimethylsiloxane is applied to a substrate or the like, a portion of the modified polydimethylsiloxane migrates to the coating film surface of the polymerizable composition due to the surface migration of the modified polydimethylsiloxane. A small amount of the modified polydimethylsiloxane that has migrated to the coating film surface migrates to a substrate not in contact with the polymerizable composition before other unreacted components bleed out of the coating film of the polymerizable composition, and the modified group of the modified polydimethylsiloxane adsorbs to the substrate surface. This forms an adsorbed film of the modified polydimethylsiloxane on the substrate surface, which is believed to exhibit water and oil repellency due to the polydimethylsiloxane moiety and suppress bleeding. Furthermore, it is believed that the organic substituent as the modifying group contains a COOH group or an OH group, thereby enabling the modified polydimethylsiloxane to have a higher adsorption effect on the substrate. Furthermore, when the organic substituent as the modifying group contains an OH group, it is believed that the adsorption effect on the substrate due to the OH group is not suppressed if the amount of polypropylene glycol groups contained in the organic substituent is not more than a certain amount.

[0046] In one embodiment, the modified polydimethylsiloxane satisfying at least one of characteristics (b) and (c) has a viscosity as measured in deuterated chloroform. １ In the H NMR spectrum, when the integral of each signal is calculated assuming that the integral of the first signal corresponding to one dimethylsiloxane repeating unit is 6, the integral of the signal (second signal) observed in the range of 4.4 to 3.2 ppm is more preferably 0.3 to 19, and even more preferably 0.3 to 17.

[0047] １ The H NMR measurement can be carried out under normal conditions. For example, 100 mg of a measurement sample is dissolved in 500 μl of deuterated chloroform, and a 5 mm diameter tube is placed in the tube. １ ​After the measurement, add 50 μl of heavy water (D ２ O) is added and the measurement is performed again under the same conditions. The signal that disappeared after the addition of heavy water is found to be a signal derived from active hydrogen bonded to a hydroxyl group or an amino group. Measurement frequency: 40-600 MHz Solvent: deuterated chloroform Measurement nuclide: １ H Accumulation number: 4 to 80 times Measurement temperature: 15 to 50°C

[0048] The modified polydimethylsiloxane (C) may be used alone or in combination of two or more.

[0049] The content of the (C) modified polydimethylsiloxane is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, relative to the total mass of the polymerizable composition. It is also preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. In some embodiments, the content of the (C) modified polydimethylsiloxane is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and even more preferably 0.2 to 3% by mass, relative to the total mass of the polymerizable composition.

[0050] The polymerizable composition of this embodiment may contain, if desired, optional components other than the above components (A) to (C), such as those described below, as necessary.

[0051] (D) Filler The polymerizable composition of this embodiment may contain (D) filler (hereinafter also referred to as "component (D)") within a range that does not impair the effects of the present invention. By containing (D) filler in the polymerizable composition, the linear expansion coefficient of the cured product obtained by curing the polymerizable composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, it can alleviate stress generated in the cured product, and long-term reliability can be improved. (D) fillers are broadly classified into inorganic fillers and organic fillers.

[0052] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one of the inorganic fillers may be used alone, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it can increase the loading amount. As the silica, amorphous silica is preferred.

[0053] The inorganic filler is preferably one whose surface has been treated with a coupling agent such as a silane coupling agent, which allows the viscosity of the polymerizable composition to fall within an appropriate range.

[0054] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The organic filler may be surface-treated. The glass transition temperature of the organic filler is preferably higher than 40°C.

[0055] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0056] In an embodiment, the average particle size of the filler is preferably 5.0 μm or less, more preferably 4.0 μm or less, and even more preferably 3.0 μm or less. In this specification, the average particle size refers to the volume-based median diameter (d ５０), or a value calculated as the number average of 50 measurements arbitrarily selected from observation images obtained by a transmission electron microscope (TEM) or a scanning electron microscope (SEM). By setting the average particle size of the filler to the upper limit or less, sedimentation of the filler can be suppressed, and the formation of coarse particles can be suppressed, thereby preventing clogging of the dispenser nozzle. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the polymerizable composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. In some embodiments of this aspect, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, and more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination. For example, a filler having an average particle size of 0.005 μm or more but less than 0.1 μm may be used in combination with a filler having an average particle size of 0.1 μm to 5.0 μm.

[0057] The content of the filler (D) in the polymerizable composition of this embodiment is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 3 to 60% by mass, relative to the total mass of the polymerizable composition. By setting the content of the filler (D) within this range, thermal cycle resistance is improved, and the viscosity of the polymerizable composition is set within an appropriate range, improving applicability in dispensers.

[0058] Photosensitizer The polymerizable composition of this embodiment may contain a photosensitizer, if desired, within the range that does not impair the effects of the present invention. The photosensitizer absorbs light energy and transmits it to the acid generator, thereby increasing the sensitivity of the acid generator to light. Examples of photosensitizers include, but are not limited to, thioxanthone derivatives, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes.

[0059] The photosensitizer may be used alone or in combination of two or more. When the polymerizable composition of this embodiment contains a photosensitizer, the content of the photosensitizer is preferably 0.1 to 1000% by mass, and more preferably 1 to 500% by mass, relative to the total mass of the acid generator.

[0060] Photoradical Initiator The polymerizable composition of this embodiment may contain a photoradical initiator, if desired, within the scope of not impairing the effects of the present invention. The photoradical initiator absorbs light to generate radicals as active species, which can reductively decompose the acid generator and promote the generation of acid from the acid generator. Examples of photoradical initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0061] The photoradical initiator may be used alone or in combination of two or more. When the polymerizable composition of this embodiment contains a photoradical initiator, the content of the photoradical initiator is preferably 10 to 200% by mass, more preferably 50 to 150% by mass, based on the total mass of the acid generator.

[0062] Thermal Radical Initiator The polymerizable composition of this embodiment may contain a thermal radical initiator, if desired, within a range that does not impair the effects of the present invention. The thermal radical initiator generates an active radical by cleavage at a predetermined temperature, which can reductively decompose the acid generator and promote the generation of an acid from the acid generator. Examples of thermal radical initiators include organic peroxides, inorganic peroxides, and azo compounds.

[0063] The thermal radical initiator may be used alone or in combination of two or more. When the polymerizable composition of this embodiment contains a thermal radical initiator, the content of the thermal radical initiator is preferably 1 to 200 mass %, more preferably 10 to 150 mass %, based on the total mass of the acid generator.

[0064] Radical Polymerizable Compound The polymerizable composition of this embodiment may contain a radically polymerizable compound to the extent that the effects of the present invention are not impaired. Depending on the type of acid generator, active species radicals may also be generated, which causes radical polymerization of the radically polymerizable compound to proceed, imparting curability and adhesiveness to the polymerizable composition. Examples of radically polymerizable compounds include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, bismaleimide compounds, styrene compounds, and polybutadiene compounds, as well as mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction). Any one type of radically polymerizable compound may be used, or two or more types may be used in combination.

[0065] Other Additives The polymerizable composition may further contain other additives, such as a stabilizer, a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, a viscosity modifier, or a flame retardant, as needed, within the scope of the present embodiment.

[0066] From the viewpoint of suppressing VOC emissions and suppressing shrinkage of the cured product, the polymerizable composition of this embodiment preferably does not substantially contain a solvent. In this specification, the phrase "the polymerizable composition does not substantially contain a solvent" means that the content of the solvent in the polymerizable composition is 1 mass % or less relative to the total mass of the polymerizable composition. Examples of the solvent include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, butyrolactone, propylene carbonate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0067] The viscosity of the polymerizable composition of this embodiment is preferably 0.5 to 100 Pa s. The viscosity can be adjusted appropriately depending on the intended use and application location of the polymerizable composition. In this specification, the viscosity of the composition is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the equipment, rotor, or measurement range used.

[0068] The polymerizable composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing components (A) to (C), and optionally other components, simultaneously or separately, while optionally applying heat treatment. The apparatus used for mixing, stirring, dispersing, etc. is not particularly limited. Examples of apparatus that can be used include a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, all equipped with a stirring and heating device. These apparatuses may also be used in appropriate combination.

[0069] The polymerizable composition of this embodiment can be a one-component polymerizable composition contained in a single container, or a two-component (or multi-component) polymerizable composition divided into two or more containers, depending on the intended use. When a two-component (or multi-component) polymerizable composition is used, the components (A) to (C) and other optional components as needed can be selected in the same manner as for a one-component composition. Furthermore, when a two-component (or multi-component) polymerizable composition is used, the components (A) to (C) and other optional components as needed can be divided into two or multiple components in any manner without particular limitation. When the composition is divided into two or multiple components in any manner, each component may contain one or more components selected from the components (A) to (C) and other optional components as needed. Alternatively, the components (A) to (C) may be contained in a single component, or a component may contain only the components (A) to (C) and / or other optional components as needed. For example, when the liquid is separated into liquid A and liquid B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (C), liquid B: component (B), liquid A: component (A) and component (C), liquid B: component (B) and component (C), liquid A: component (A), liquid B: component (B), component (C), and component (D), liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), liquid B: component (B) and component (C). When components (A) to (C) are contained in liquid A and other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered as the polymerizable composition of this embodiment. On the other hand, when the components (A) to (C) are contained in separate liquids, the liquids can be considered as a combination of the polymerizable composition of this embodiment. Examples of the case where the components (A) to (C) are contained in separate liquids include a polymerizable composition in which the components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (C).

[0070] The polymerizable composition obtained in this manner is photocurable, thermocurable, or photo- and thermo-curable, depending on the type of acid generator contained in the polymerizable composition. Photocuring of the polymerizable composition is carried out, for example, by irradiating the polymerizable composition with UV light. Thermal curing of the polymerizable composition is carried out, for example, at a temperature of 100°C. When the polymerizable composition is used to manufacture a semiconductor module (e.g., an optical sensor module such as a camera module) containing components that deteriorate under high temperature conditions, the thermal curing temperature of the polymerizable composition is preferably 60 to 90°C. The thermal curing time depends on other curing conditions, but may be, for example, 30 to 120 minutes. When the polymerizable composition is photo- and thermo-curable, for example, the polymerizable composition can be pre-cured by curing with light (UV) and then fully cured by curing with heat.

[0071] The polymerizable composition of this embodiment can be used, for example, as an adhesive, sealant, or damming agent for fixing, adhering, or protecting components, and as a raw material thereof, and is suitable as a one-component type. Here, the damming agent is formed, for example, on the periphery of a substrate before sealing multiple semiconductor chips or the like on the substrate with a low-viscosity filler or the like. The formation of a dam by this damming agent can prevent the subsequent outflow of the low-viscosity filler that seals the multiple semiconductor chips. Furthermore, adhesives containing the polymerizable composition of this embodiment can also provide good bonding to engineering plastics, ceramics, and metals.

[0072] The method for applying the polymerizable composition is not particularly limited, and for example, the composition can be applied to a desired portion of a component such as a substrate by a known printing method, dispensing method, or coating method. Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, and flexographic printing. Dispensing methods include, but are not limited to, methods using a jet dispenser or an air dispenser. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating. In one embodiment, the method for applying the polymerizable composition is preferably a method using an air dispenser.

[0073] [Adhesive or Sealant] An adhesive or sealant according to one embodiment of the present invention comprises the polymerizable composition of the above-described embodiment. This adhesive or sealant provides excellent fixation, bonding, or protection for general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics (e.g., alumina, aluminum nitride, beryllium oxide, etc.), and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect components constituting semiconductor devices or electronic components. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules, other semiconductor modules, and integrated circuits. The adhesive or sealant according to this embodiment is preferably used to fix, bond, or protect components constituting optical sensor modules such as camera modules.

[0074] The adhesive or sealant of this embodiment can be a one-component adhesive or sealant contained in a single container, or a two-component (or multi-component) adhesive or sealant divided into two or more containers, depending on its intended use. When a two-component (or multi-component) adhesive or sealant is used, the components (A) to (C) and other optional components as needed can be selected in the same manner as for a one-component adhesive or sealant. Furthermore, when a two-component (or multi-component) adhesive or sealant is used, the components (A) to (C) and other optional components as needed can be divided into two or multiple components in any manner without particular limitation. When divided into two or multiple components in any manner, each component may contain one or more components selected from the components (A) to (C) and other optional components as needed. The components (A) to (C) may be contained in a single component, or a component may contain only the components (A) to (C) and / or other optional components as needed. For example, when the liquid is divided into liquid A and liquid B, the division may be liquid A: component (A), liquid B: component (B) and component (C), or liquid A: component (A) and component (C), liquid B: component (B), or liquid A: component (A) and component (C), liquid B: component (B) and component (C), or liquid A: component (A), liquid B: component (B), component (C), and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), or liquid B: component (B) and component (C). When components (A) to (C) are contained in liquid A and other components are contained in liquid B, only liquid A, or a combination of liquid A and liquid B, can be considered as the adhesive or sealant of this embodiment. On the other hand, when the components (A) to (C) are contained in separate liquids, the liquids can be collectively regarded as the adhesive or sealant of this embodiment. Examples of the case where the components (A) to (C) are contained in separate liquids include an adhesive or sealant in which the components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (C).

[0075] [Cured Product of Polymerizable Composition, Adhesive, or Sealant] Another embodiment of the present invention is a cured product obtained by curing the polymerizable composition or the adhesive or sealant of the above-described embodiment. Bleeding is suppressed around an adherend to which the cured product is adhered.

[0076] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to one embodiment of the present invention includes the cured product according to the above-described embodiment. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, and electronic devices. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, optical sensor modules, other semiconductor modules, and integrated circuits. Examples of optical sensors include, but are not limited to, photodiodes, photo ICs, photomultiplier tubes (PMTs), phototubes, image sensors, spectroscopes / spectroscopic sensors, infrared sensors, ultraviolet / flame sensors, X-ray sensors, radiation sensors, electron / ion sensors, and distance / position sensors.

[0077] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0078] [Preparation of Polymerizable Compositions] Polymerizable compositions of the Examples and Comparative Examples were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Tables 2-1 to 2-5. In Tables 2-1 to 2-5, the amount of each component is expressed in parts by mass (unit: g). The components used in the Examples and Comparative Examples are as follows:

[0079] (A) Cationic Polymerizable Compounds (A-1): Hydrogenated bisphenol A diglycidyl ether (product name: jER YX8000, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 205 g / eq) (A-2): Special epoxy resin (product name: AER9000, manufactured by Asahi Kasei Corporation, polyether type epoxy, epoxy equivalent: 380 g / eq) (A-3): 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (product name: CELLOXIDE (registered trademark) 2021P, manufactured by Daicel Corporation, alicyclic epoxy, epoxy equivalent: 130 g / eq) (A-4): 1,2-epoxytetradecane (product name: TD-EX, manufactured by Yokkaichi Chemical Co., Ltd., monofunctional epoxy, epoxy equivalent: 212 g / eq) (A-5): Special epoxy resin (product name: HiREM-2, manufactured by Shikoku Chemical Industries, Ltd., epoxy equivalent: 80 g / eq) (A-6): 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (product name: OXT-221, manufactured by Toagosei Co., Ltd., oxetane equivalent: 107 g / eq) (B) Acid generator (B-1): 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (product name: BLUESIL (registered trademark) PI 2074, manufactured by ELKEM SILICONES, photoacid generator) (B-2): Sulfonium salt-based acid generator (product name: VC-1FG, manufactured by San-Apro Co., Ltd., photoacid generator) (B-3): Borate-based quaternary ammonium salt (product name: CXC-1821, manufactured by King Industries, Inc., thermal acid generator)

[0080] (C) Modified polydimethylsiloxane (component (C)) (C') Modified polydimethylsiloxane other than component (C) (component (C')) The modified polydimethylsiloxanes shown in Table 1 below were used as components (C) and (C'). １ The results of the 1 H NMR measurement, Fourier transform infrared spectroscopy (FT-IR) measurement, and acidity measurement are shown in Table 1.

[0081]

[0082] In Table 1, "Ph" represents a phenyl group, and "Me" represents a methyl group. In Table 1, "[(third signal) / 3] / {[(second signal)-(third signal)] / 4}" represents [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4} in formula (1).

[0083] (D) Filler (Component (D)) (D-1): Surface-treated silica filler (product name: SE5200SEE, average particle size 2 μm, manufactured by Admatechs Co., Ltd.) (D-2): Silica filler (product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated fumed silica, manufactured by Cabot Corporation) (E) Other optional components (E-1): Dicetyl peroxydicarbonate (product name: Perkadox 24L, manufactured by Kayaku Nouryon Co., Ltd., thermal radical initiator) (E-2): 2,4-diethylthioxanthone (DETX) (photosensitizer)

[0084] [Modified polydimethylsiloxane １ 1H NMR Measurement] 100 mg of a measurement sample of various modified polydimethylsiloxanes was dissolved in 500 μL of deuterated chloroform, and １ The sample was placed in a sample tube for H NMR and measured under the following conditions. After the measurement, 50 μL of heavy water (D ２ O) was added and measurement was carried out again under the same conditions. The integral value of each signal is shown in Table 1, assuming that the integral value of the signal from 0.3 to -0.3 ppm derived from chloroform is 6. Measurement equipment: Oxford instrument Pulsar HF Measurement frequency: 60 MHz Solvent: deuterated chloroform Measurement nuclide: １ H Measurement temperature: 37°C Number of measurements: 32

[0085] The signal assignment examples under the above measurement conditions are as follows: 0.3 to −0.3 ppm: hydrogen atom connected to a carbon atom adjacent to a Si atom (−Si(CH ３ ) ２-) 4.4 to 3.2 ppm: Signals from a hydrogen atom connected to a carbon adjacent to an OH group or an oxygen atom of an ether (e.g., -O-CH ２ CH ２ —O—, —O—CH ２ CH (CH ３ ) —O—, —CH ２ 1.25 to 0.95 ppm (d, approximately 6 Hz): Signals from hydrogen atoms (-CH) of methyl groups in polypropylene glycol chains ２ CH (CH ３ Under the above measurement conditions, the signal derived from D ２ Signals that disappear upon addition of O: Signals derived from hydrogen atoms of OH or NH groups

[0086] [Fourier transform infrared spectroscopy (FT-IR) measurement of modified polydimethylsiloxanes] Fourier transform infrared spectroscopy (FT-IR) measurement of various modified polydimethylsiloxanes was carried out under the following conditions, and the C═O stretching vibration of carboxylic acid (approximately 1715 cm －１ ) and the presence or absence of alcoholic OH bending vibration (approximately 1360-1340 cm －１ The presence or absence of α-tocopherol was confirmed. The results are shown in Table 1. Measuring device: Perkin-Elmer FT-IR Spectrometer Spectrum 3 Measuring method: ATR method

[0087] [Measurement of Acidity of Modified Polydimethylsiloxanes] 100 mg of each modified polydimethylsiloxane sample was dissolved in 200 μL of isopropyl alcohol (IPA), 200 μL of pure water was added, and the mixture was shaken well. pH test paper was immersed in the resulting liquid and the pH was determined. Macherey Nagel #90204 Universal indicator paper was used as the pH test paper. The results are shown in Table 1.

[0088] In the examples and comparative examples, the properties of the polymerizable compositions were measured as follows.

[0089] [Bleeding Evaluation] 1.5 mg of each of the polymerizable compositions of the Examples and Comparative Examples was potted onto a ceramic substrate that had been plasma-treated with argon (Ar) gas using a dispenser. The bleed length under two conditions was measured using a CCD camera (N = 3 pcs × 2 sides). The results are shown in Tables 2-1 to 2-5. Condition 1: The bleed length on the ceramic substrate after potting and leaving it at room temperature (20°C to 25°C) for 60 minutes. Condition 2: The bleed length on the ceramic substrate after potting and leaving it at room temperature (20°C to 25°C) for 60 minutes, and then thermally curing the polymerizable composition at 80°C for 60 minutes. Note that the bleed lengths shown in Tables 2-1 to 2-5 are measured at a bleed length measurement limit of 3000 μm, and bleed lengths exceeding this measurement limit are recorded as >3000 μm.

[0090]

[0091] It can be seen that the polymerizable compositions of Examples 1 to 19 containing a modified polydimethylsiloxane (C) that satisfies at least one of characteristics (a), (b), and (c) exhibited significantly reduced bleeding under both Condition 1 and Condition 2, compared to the polymerizable compositions of Comparative Examples 1 and 7 to 11 that did not contain a modified polydimethylsiloxane (C), and the polymerizable compositions of Comparative Examples 2 to 6 that contained a modified polydimethylsiloxane other than component (C) (C').

[0092] The present invention relates to a polymerizable composition that is at least photocurable or thermosetting and can suppress the bleeding phenomenon, and is particularly useful as an adhesive or sealant used for fixing, adhering, or protecting components of miniaturized or highly integrated semiconductor modules.

[0093] The disclosure of Japanese Patent Application No. 2024-056011 (filing date: March 29, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. (A) a cationically polymerizable compound; (B) an acid generator; and (C) a modified polydimethylsiloxane satisfying at least one of the following characteristics (a), (b), and (c): (a) an organic substituent containing a COOH group is bonded to the polydimethylsiloxane directly or via a linker; (b) an organic substituent containing an OH group and optionally an ether group is bonded to the polydimethylsiloxane directly or via a linker, and when the organic substituent contains an ether group, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units in the organic substituent is less than 0.3; (c) a cationically polymerizable compound (A) having a cationically polymerizable compound (B ... １ In the H NMR spectrum, there are signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, there are signals or no signals in the range of 1.25 to 0.95 ppm, and there are signals in the range of 13 to 0 ppm. ２ A polymerizable composition having a signal that disappears upon addition of O, and a value calculated by the following formula (1) is less than 0.3, the polymerizable composition comprising: Formula (1): [(integral value of signals in the range of 1.25 to 0.95 ppm) / 3] / {[(integral value of signals in the range of 4.4 to 3.2 ppm)-(integral value of signals in the range of 1.25 to 0.95 ppm)] / 4}.

2. The polymerizable composition according to claim 1, wherein the cationically polymerizable compound (A) includes a compound having an epoxy group and a compound having an oxetanyl group.

3. The polymerizable composition according to claim 1 or 2, wherein the content of the (C) modified polydimethylsiloxane is 0.01 to 5% by mass relative to the total mass of the polymerizable composition.

4. The polymerizable composition according to any one of claims 1 to 3, further comprising (D) a filler.

5. The polymerizable composition according to any one of claims 1 to 4, wherein components (A) to (C) are contained in a single container.

6. The polymerizable composition according to any one of claims 1 to 4, wherein components (A) to (C) are separated into two or more containers.

7. An adhesive or sealant comprising the polymerizable composition according to any one of claims 1 to 6.

8. The adhesive or sealant according to claim 7, which is used to fix, bond or protect an optical sensor module or a component that constitutes the optical sensor module.

9. A cured product obtained by curing the polymerizable composition according to any one of claims 1 to 6, or the adhesive or sealant according to claim 7 or 8.

10. A semiconductor device or electronic part comprising the cured product according to claim 9.

11. The semiconductor device or electronic component according to claim 10, which is an optical sensor module.

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