WO2025205910A1 - Polymerizable composition, adhesive, sealing material, cured product, semiconductor device, and electronic component - Google Patents

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

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

Currently, adhesives, sealants, etc. containing curable resin compositions are often used to assemble and mount components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability.

The development of photocurable and/or low-temperature curable resin compositions is progressing. For example, Patent Documents 1 and 2 disclose photocurable and low-temperature curable cationically curable resin compositions.

Re-table 2017/094584 publication Japanese Patent Application Laid-Open No. 2021-147584

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 called "bleed." If the bleed comes into contact with the metal wiring on the board, it can cause electrical defects, reducing the reliability of the semiconductor module. In particular, inner bleed, which occurs from uncured parts of the adhesive, tends to progress when the adhesive coating is left at room temperature and/or when it is thermally cured, and the bleed length tends to increase.

In recent years, there has been a growing demand for electronic components such as semiconductor chips to be increasingly smaller and more highly integrated, resulting in shorter distances to the wiring areas located around the electronic components. Semiconductor modules equipped with such smaller and more highly integrated electronic components pose a challenge, as bleeding increases the risk of contact between the bleeding and the wiring areas.

The present invention therefore aims to provide at least a photocurable or thermosetting polymerizable composition and adhesive that can suppress the bleeding phenomenon.

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 that satisfies at least one of the following characteristics (a), (b), and (c):
(a) an organic substituent containing a COOH group is bonded to 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) In ^{a 1} H NMR spectrum measured in deuterated chloroform, it has signals in the ranges of 0.3 to −0.3 ppm and 4.4 to 3.2 ppm, has or has no signal in the range of 1.25 to 0.95 ppm, has a signal in the range of 13 to 0 ppm that disappears upon addition of D ₂ 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}
A polymerizable composition comprising:
[2] The polymerizable composition according to the above [1], wherein the (A) cationically polymerizable compound includes a compound having an epoxy group and a compound having an oxetanyl group.
[3] The polymerizable composition according to the above [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 [1] to [3], further comprising (D) a filler.
[5] The polymerizable composition according to any one of the above [1] to [4], wherein the components (A) to (C) are contained in a single container.
[6] The polymerizable composition according to any one of the above [1] to [4], wherein the 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 optical sensor module.
[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.

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

[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 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) In ¹ H NMR measured in deuterated chloroform, it has signals in the ranges of 0.3 to −0.3 ppm and 4.4 to 3.2 ppm, has or has no signal in the range of 1.25 to 0.95 ppm, has a signal in the range of 13 to 0 ppm that disappears upon addition of D ₂ 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.

(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.

In this specification, a compound having an epoxy group refers to a compound having at least one epoxy group in its 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 according to the type of skeleton into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds.

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 certain embodiments, 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.

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

Specific examples of cationic polymerizable compounds 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-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexylmethyl)adipate 2,2-bis(3,4-epoxycyclohexane), propane-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-epoxy Cyclohexane, 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-hydroxymethyl oxetane, 2-ethylhexyl oxetane, (3-ethyloxetan-3-yl) methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl Examples of vinyl ethers include, but are not limited to, ethyl-3-(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.

Commercially available cationic 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; and EPICLON (registered trademark) 830-S and EXA-830 manufactured by DIC Corporation. LVP, EXA-835LV; EPICLON (registered trademark) HP-4032D, HP-720H manufactured by DIC Corporation; 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 GLYCILOR (registered trademark) ED-5 manufactured by ADEKA Corporation 09E, ED-509S; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; AER-9000 manufactured by Asahi Kasei Corporation; jER YX7400N manufactured by Mitsubishi Chemical Corporation; 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, 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.

Any one of the cationically polymerizable compounds may be used, or two or more may be used in combination.

The cationic polymerizable group equivalent of the cationic 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.

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

From the viewpoint of the adhesive strength of the polymerizable composition, the content of component (A) is preferably 10 to 95 mass %, and more preferably 20 to 90 mass %, relative to the total mass of the polymerizable composition.

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 exposure to light or heat, thereby promoting polymerization of the cationically polymerizable compound. Examples of the acid generator include various onium salts having a counter anion such as 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} ^] ₋ ⁽ wherein R ¹ is 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 greater, multiple R ^1s may be the same or different), and an iodonium cation, sulfonium cation, ammonium cation, phosphonium cation, or the like as the cation moiety.

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.

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-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo triarylsulfonium compounds such as so-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]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 compounds 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 thereof include trialkylsulfonium such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

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. Examples include sulfolinium, piperidinium such as N,N'-diethylpiperidinium, 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.

Examples of phosphonium cations 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.

Specific examples of iodonium salt acid generators include:
photoacid generators which 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;
photoacid generators which are phosphate-based iodonium salts, such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF), and bis(C _10-14 -alkylphenyl)iodonium hexafluorophosphate (e.g., WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (here, IK-1 manufactured by San-Apro 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 (for example, WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.);
a photoacid generator which is a gallate-based iodonium salt such as IK-1FG (manufactured by San-Apro Co., Ltd.) (wherein IK-1FG can also be used as a thermal acid generator);
Examples of photoacid generators include, but are not limited to, 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).

Specific examples of sulfonium salt acid generators include, but are not limited to, borate-based sulfonium salt photoacid generators (products manufactured by San-Apro Ltd. such as CPI-110B, CPI-310B, and CPI-410B), phosphate-based sulfonium salt photoacid generators (products manufactured by San-Apro Ltd. such as CPI-210S, VC-1S, and CPI-410S), phosphate-based sulfonium salt thermal acid generators (products manufactured by San-Apro Ltd. such as TA-100), gallate-based sulfonium salt photoacid generators (products manufactured by San-Apro Ltd. such as CPI-310FG and VC-1FG), and gallate-based sulfonium salt thermal acid generators (products manufactured by San-Apro Ltd. such as TA-100FG).

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

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

(C) Modified Polydimethylsiloxane The polymerizable composition of this embodiment contains (C) a modified polydimethylsiloxane (hereinafter also referred to as "component (C)"). In this embodiment, the modified polydimethylsiloxane (C) satisfies at least one of the following characteristics (a), (b), and (c):
(a) An organic substituent containing a COOH group is bonded to 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) In ^{a 1} H NMR spectrum measured in deuterated chloroform, it has signals in the ranges of 0.3 to −0.3 ppm and 4.4 to 3.2 ppm, has or has no signal in the range of 1.25 to 0.95 ppm, has a signal in the range of 13 to 0 ppm that disappears upon addition of D ₂ O, and the value calculated from 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}

More specifically, the modified polydimethylsiloxane is represented by the formula:

The modified polydimethylsiloxane has a structure in which an organic substituent is introduced as a modifying group into the side chain and/or terminal of a polydimethylsiloxane main chain consisting of dimethylsiloxane repeating units represented by the formula (I), either directly or via a linker such as an alkyl group or alkylene group. Here, "an organic substituent is introduced into the side chain of the polydimethylsiloxane main chain" means that some methyl groups in the polydimethylsiloxane main chain are substituted with organic substituents. "an organic substituent is introduced into the terminal of the polydimethylsiloxane main chain" means that the terminal of the polydimethylsiloxane main chain (e.g., a methyl group or -OSi( _CH3 ) ₃ ) is substituted with an organic substituent. The position at which the modifying group is introduced into the modified polydimethylsiloxane may be the side chain, the terminal (one terminal or both terminals), or both the side chain and the terminal. The modified polydimethylsiloxane also includes 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.

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

Examples of modified polydimethylsiloxanes in which the organic substituents contain COOH groups include those commercially available under the names carboxyl-modified polydimethylsiloxane or carboxyl-modified silicone. 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.

Whether or not the organic substituent of the modified polydimethylsiloxane contains a COOH group can also be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and observing the presence or absence of an IR spectrum at about 1715 cm ⁻¹ derived from the C═O stretching vibration of carboxylic acid.

In the modified polydimethylsiloxane according to feature (b) above, the organic substituent contains an OH group and optionally an ether group. 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.

Examples of modified polydimethylsiloxanes in which the organic substituents contain OH groups but not ether groups include those commercially available under the names carbinol-modified polydimethylsiloxanes or carbinol-modified silicones. Examples of commercially available products of this type include, but are not limited to, products sold by Shin-Etsu Chemical Co., Ltd. under the names: X-22-4039, X-22-4015, KF-6000, KF-6001, KF-6002, KF-6003, X-22-170BX, and X-22-170DX.

Examples of modified polydimethylsiloxanes in which the above-mentioned organic substituents contain OH groups and ether groups include those called polyether-modified polydimethylsiloxanes or polyether-modified silicones, in which the polyether group terminates in an OH group. Examples of commercially available products 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 n. In the INCI nomenclature, "PEG-(number) dimethicone" is abbreviated as "PEG-(n) DIMETHICONE." Examples of such polypropylene glycol repeating units in a ratio of 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), and PEG-10 dimethicone (sold by Shin-Etsu Chemical Co., Ltd., product name: KF-6043).

Reactive silicones whose hydroxyl values are disclosed in catalogs 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 or not the organic substituent of the modified polydimethylsiloxane contains an OH group can also be confirmed by measuring the modified polydimethylsiloxane by Fourier transform infrared spectroscopy (FT-IR) and observing the presence or absence of an IR spectrum at about 1360 to 1340 cm ⁻¹ due to the deformation vibration of alcoholic OH.

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, if it is clear that the modified polydimethylsiloxane contains an OH group and an ether group but does not contain a polypropylene glycol repeating unit, the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units will be 0, satisfying feature (b). If a specific structure is not disclosed, as described below with respect to feature (c), it can be calculated based on the ^1H NMR spectrum of the modified polydimethylsiloxane measured in deuterated chloroform. Specifically, the value calculated using the following formula (1) based on the ^1H NMR spectrum of the modified polydimethylsiloxane measured in deuterated chloroform can be considered to be the ratio of the number of polypropylene glycol repeating units to the number of polyethylene glycol repeating units.
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}

Some commercially available modified polydimethylsiloxanes do not disclose the detailed structure of the modifying group. Furthermore, some commercially available additives, such as surfactants, surface conditioners, leveling agents, antifoaming agents, wetting agents, and dispersants, are classified as modified polydimethylsiloxanes, even though they are not explicitly referred to as modified polydimethylsiloxanes or their structures are not disclosed. In such cases, the modified polydimethylsiloxanes of this embodiment are those that, in their ^1H NMR spectrum measured in deuterated chloroform, have signals in the ranges of 0.3 to -0.3 ppm and 4.4 to 3.2 ppm, have or do not have a signal in the range of 1.25 to 0.95 ppm, and have a signal in the range of 13 to 0 ppm that disappears upon addition of _D2O , and for which the value calculated from 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 signal derived from a hydrogen atom (-Si(C H ₃ ) ₂ -) connected to a carbon atom adjacent to a Si atom.
The signal observed in the range of 4.4 to 3.2 ppm (hereinafter also referred to as "second signal") is a signal derived from a hydrogen atom connected to a carbon adjacent to an OH group or an oxygen atom of an ether (e.g., -O-C H ₂ C H ₂ -O-, -O-C H ₂ C H (CH ₃ )-O-, -C H ₂ -OH).
The signal observed in the range of 1.25 to 0.95 ppm (hereinafter also referred to as "third signal") is a signal derived from a hydrogen atom (-CH ₂ CH(C H ₃ )-O-) of a methyl group in a polypropylene glycol chain as a polyether modifying group.
The signal observed in the range of 13 to 0 ppm and disappearing upon addition of D ₂ O (hereinafter also referred to as "fourth signal") can be presumed to be a signal derived from the hydrogen atom of an OH group or an NH group.

Signals that disappear upon addition of D ₂ O are usually observed in the range of 13 to 0 ppm. Among these, signals observed in the range of 3 to 2 ppm and that disappear upon addition of D ₂ O can be presumed to be signals derived from hydrogen atoms of OH groups.

Whether the signal that disappears upon addition of D ₂ O is a signal derived from a hydrogen atom of an OH group or an NH group can also be estimated by, for example, the following method.
Fourier transform infrared spectroscopy (FT-IR) measurement In addition to the above ¹ H NMR measurement, the presence or absence of an IR spectrum at approximately 1360 to 1340 cm ⁻¹ derived from the deformation vibration of alcoholic OH groups can be observed by Fourier transform infrared spectroscopy (FT-IR) measurement of the modified polydimethylsiloxane, and it can be assumed that the signal that disappears upon addition of D ₂ O is a signal derived from the hydrogen atom of the OH group.
Measurement of Acidity In addition to the above ^1H NMR measurement, measurement of the acidity of modified polydimethylsiloxane allows estimation of whether the signal that disappears upon addition of _D2O is derived from the hydrogen atom of an OH group or an NH group. 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 solution is shaken well, and the pH of the liquid is measured. If the pH is 3 to 7, the signal that disappears upon addition of _D2O can be estimated to be derived from the hydrogen atom of an OH group. If the pH is 8 or higher, which is basic, the signal that disappears upon addition of _D2O can be estimated to be derived from the hydrogen atom of an NH group.

In the above characteristic (c), the value calculated from formula (1) is less than 0.3, which 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 observed in the range of 0.3 to −0.3 ppm (first signal) is attributed to the underlined hydrogen atom of the dimethylsiloxane repeating unit —O—Si(C H ₃ ) ₂ —.
The signal (second signal) observed in the range of 4.4 to 3.2 ppm is attributed to the underlined hydrogen atoms of the polyethylene glycol repeating unit -O-C H ₂ C H ₂ -O- and the underlined hydrogen atoms of the polypropylene glycol repeating unit -O-C H ₂ C H (CH ₃ )-O-,
The signal observed in the range of 1.25 to 0.95 ppm (third signal) is assigned to the underlined hydrogen atom of the polypropylene glycol repeating unit -CH ₂ CH(C H ₃ )-O-.
This is the assumption.
Under the above assumptions, when the integral value of each signal is calculated assuming that the integral value 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):
Equation (2): (integral value 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):
Equation (3): [(integral value of the second signal) - (integral value 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 value of the third signal)/3]/{[(integral value of the second signal)-(integral value of the third signal)]/4}

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

In the polymerizable composition of this embodiment, by including (C) a modified polydimethylsiloxane that satisfies at least one of characteristics (a), (b), and (c), bleeding is suppressed after application to a substrate or the like, not only during thermal curing but also when left at room temperature. The reason why bleeding is suppressed by including (C) a modified polydimethylsiloxane in the polymerizable composition 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 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 surface migrates to a substrate that is not in contact with the polymerizable composition, before other unreacted components seep out of the coating of the polymerizable composition, and the modifying group of the modified polydimethylsiloxane adsorbs to the surface of the substrate. This is thought to form an adsorption film of modified polydimethylsiloxane on the substrate surface, resulting in water- and oil-repellent properties attributable to the polydimethylsiloxane portion and suppressing bleeding. Furthermore, it is thought that the organic substituent as the modifying group containing a COOH group or an OH group can provide a higher adsorption effect of the modified polydimethylsiloxane to the substrate. Furthermore, when the organic substituent as the modifying group contains an OH group, it is thought that the adsorption effect of the OH group to the substrate is not suppressed if the amount of polypropylene glycol groups contained in the organic substituent is below a certain amount.

In one embodiment, a modified polydimethylsiloxane satisfying at least one of features (b) and (c) is one in which, in ^{a 1} H NMR spectrum measured in deuterated chloroform, the integral of each signal (second signal) observed in the range of 4.4 to 3.2 ppm is preferably 0.3 to 19, and even more preferably 0.3 to 17, when the integral of the first signal corresponding to one dimethylsiloxane repeating unit is set to 6 and the integral of each signal is calculated.

^1H NMR measurements can be performed under normal conditions. For example, 100 mg of a measurement sample is dissolved in 500 μl of deuterated chloroform and placed in a 5 mm diameter ^1H NMR sample tube, and measurements are performed under the following conditions. After the measurement, 50 μl of heavy water ( _D2O ) is added to the sample tube, and measurements are performed again under the same conditions. The signal that disappears 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 count: 4 to 80 times Measurement temperature: 15 to 50°C

(C) Modified polydimethylsiloxane may be used alone or in combination of two or more types.

The content of (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 (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.

If desired, the polymerizable composition of this embodiment may contain optional components other than the above components (A) to (C), such as those described below, as needed.

(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.

The inorganic filler is not particularly limited as long as it is made of granular 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 these inorganic fillers may be used alone, or two or more may be used in combination. Silica filler is preferred as the inorganic filler, as it allows for a high loading. Amorphous silica is preferred as the silica.

It is preferable that the surface of the inorganic filler be treated with a coupling agent such as a silane coupling agent. This allows the viscosity of the polymerizable composition to be within an appropriate range.

Examples of organic fillers include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The organic filler may be surface-treated. The glass transition point of the organic filler is preferably above 40°C.

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

In some embodiments, 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 ) measured by laser diffraction in accordance with ISO-13320 (2009), or the value calculated as the number average of 50 measurements arbitrarily selected from observation images acquired with 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, more preferably 0.1 μm to 3.0 μm. Fillers with different average particle sizes may be used in combination, for example, a filler with an average particle size of 0.005 μm or more and less than 0.1 μm may be used in combination with a filler with an average particle size of 0.1 μm to 5.0 μm.

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 keeping the content of the filler (D) within this range, thermal cycle resistance is improved, and the viscosity of the polymerizable composition is kept within an appropriate range, improving applicability in dispensers.

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.

Any one of the photosensitizers may be used, or two or more may be used in combination. 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.

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.

Any one of the photoradical initiators may be used, or two or more may be used in combination. When the polymerizable composition of this embodiment contains a photoradical initiator, the content of the photoradical initiator is preferably 10 to 200% by mass, and more preferably 50 to 150% by mass, relative to the total mass of the acid generator.

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.

Any one of the thermal radical initiators may be used, or two or more may be used in combination. When the polymerizable composition of this embodiment contains a thermal radical initiator, the content of the thermal radical initiator is preferably 1 to 200% by mass, and more preferably 10 to 150% by mass, relative to the total mass of the acid generator.

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.

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.

The polymerizable composition of this embodiment preferably contains substantially no solvent, from the viewpoint of suppressing VOC emissions and shrinkage of the cured product. In this specification, "the polymerizable composition contains substantially no solvent" means that the content of solvent in the polymerizable composition is 1 mass % or less relative to the total mass of the polymerizable composition. Examples of solvents 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.).

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 restrictions on the equipment, rotor, or measurement range used.

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 applying heat treatment as necessary. There are no particular limitations on the equipment used for mixing, stirring, dispersing, etc. Examples of equipment 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 devices may also be used in appropriate combinations.

Depending on the intended use, 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 separated into two or more containers. 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 way 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 separated into two or multiple components in any manner without particular restrictions. When separating 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. 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 components (A) to (C) are contained in separate liquids, the liquids can be considered together to be the polymerizable composition of this embodiment. An example of a case in which components (A) to (C) are contained in separate liquids is a polymerizable composition in which components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

The polymerizable composition obtained in this manner may be 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. Thermocuring of the polymerizable composition is carried out, for example, at a temperature of 100°C. The thermocuring temperature of the polymerizable composition is preferably 60 to 90°C when the polymerizable composition is used to manufacture semiconductor modules (e.g., optical sensor modules such as camera modules) that include components that deteriorate under high temperature conditions. The thermocuring 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.

The polymerizable composition of this embodiment can be used, for example, as an adhesive, sealant, or damming agent for fixing, adhering, or protecting components, as well as a raw material for these, and is suitable as a one-component type. Here, the damming agent is formed, for example, around the periphery of the 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 enable good bonding to engineering plastics, ceramics, and metals.

The method for applying the polymerizable composition is not particularly limited, and for example, it can be applied to the 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 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.

[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.

Depending on the intended use, 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 separated into two or more containers. 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 way 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 separated into two or multiple components in any manner without particular restrictions. When separated 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. Components (A) to (C) may be contained in a single component, or a component may be a component consisting solely of 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 components (A) to (C) are contained in separate liquids, the liquids can be considered together to be the adhesive or sealant of this embodiment. An example of a case in which components (A) to (C) are contained in separate liquids is an adhesive or sealant in which components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

[Cured product of polymerizable composition, adhesive or sealant]
The cured product according to another embodiment of the present invention is a cured product obtained by curing the polymerizable composition according to the above embodiment or the adhesive or sealant according to the above embodiment. Bleeding is suppressed around an adherend to which the cured product is adhered.

[Semiconductor devices, electronic components]
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.

The present invention will be explained 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 percentages indicate parts by mass and percentages by mass unless otherwise specified.

[Preparation of polymerizable composition]
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:

(A) Cationic Polymerizable Compound (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 Synthetic Co., Ltd., monofunctional epoxy, epoxy equivalent: 212 g/eq)
(A-5): Special epoxy resin (product name: HiREM-2, manufactured by Shikoku Chemicals Co., 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)

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

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).

(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)

[ ^1H NMR Measurement of Modified Polydimethylsiloxane]
100 mg of a measurement sample of each modified polydimethylsiloxane was dissolved in 500 μL of deuterated chloroform and placed in a 5 mm diameter ¹ H NMR sample tube, and measurement was performed under the following conditions. After the measurement, 50 μL of heavy water (D ₂ O) was added to the sample tube, and measurement was performed again under the same conditions. The integral value of each signal, where the integral value of the chloroform-derived signal from 0.3 to -0.3 ppm is set to 6, is shown in Table 1.
Measurement equipment: Oxford instrument Pulsar HF
Measurement frequency: 60 MHz
Solvent: deuterated chloroform Measurement nuclide: ¹ H
Measurement temperature: 37℃
Number of times accumulated: 32

An example of the assignment of each signal under the above measurement conditions is as follows:
0.3 to -0.3 ppm: signal derived from a hydrogen atom (-Si(C H ₃ ) ₂ -) connected to a carbon atom adjacent to an Si atom 4.4 to 3.2 ppm: signal derived from a hydrogen atom connected to a carbon adjacent to an OH group or an oxygen atom of an ether (for example, -O-C H ₂ C H ₂ -O-, -O-C H ₂ C H (CH ₃ )-O-, -C H ₂ -OH) 1.25 to 0.95 ppm (d, approximately 6 Hz): signal derived from a hydrogen atom of a methyl group in a polypropylene glycol chain (-CH ₂ CH(C H ₃ )-O-) Signals that appear in the range of 9.0 to 0.5 ppm under the above measurement conditions and disappear upon addition of D ₂ O: signals derived from a hydrogen atom of an OH group or an NH group

[Fourier transform infrared spectroscopy (FT-IR) measurement of modified polydimethylsiloxane]
Fourier transform infrared spectroscopy (FT-IR) measurements were performed on various modified polydimethylsiloxanes under the following conditions to confirm the presence or absence of the carboxylic acid C=O stretching vibration (approximately 1715 cm ^-1 ) and the alcoholic OH deformation vibration (approximately 1360 to 1340 cm ^-1 ). The results are shown in Table 1.
Measurement equipment: Perkin-Elmer FT-IR Spectrometer Spectrum 3
Measurement method: ATR method

[Measurement of acidity of modified polydimethylsiloxane]
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.

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

[Bleeding evaluation]
Using a dispenser, 1.5 mg of the polymerizable compositions of the Examples and Comparative Examples were potted onto a ceramic substrate that had been plasma-treated with argon (Ar) gas. The bleed lengths under the following two conditions were 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.
In addition, with regard to the bleeding lengths shown in Tables 2-1 to 2-5, since the measurement limit for bleeding length is 3000 μm, bleeding lengths exceeding the measurement limit are recorded as >3000 μm.

The polymerizable compositions of Examples 1 to 19 containing (C) a modified polydimethylsiloxane that satisfies at least one of characteristics (a), (b), and (c) showed 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 the (C) modified polydimethylsiloxane, and the polymerizable compositions of Comparative Examples 2 to 6 that contained (C') a modified polydimethylsiloxane other than component (C).

The present invention relates to a polymerizable composition that is at least photocurable or thermosetting and can suppress bleeding, and is particularly useful as an adhesive or sealant used to fix, bond, or protect components in miniaturized or highly integrated semiconductor modules.

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

Claims (11)

(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 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) In ^{a 1} H NMR spectrum measured in deuterated chloroform, it has signals in the ranges of 0.3 to −0.3 ppm and 4.4 to 3.2 ppm, has or has no signal in the range of 1.25 to 0.95 ppm, has a signal in the range of 13 to 0 ppm that disappears upon addition of D ₂ 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}
A polymerizable composition comprising: The polymerizable composition according to claim 1, wherein the (A) cationically polymerizable compound includes a compound having an epoxy group and a compound having an oxetanyl group. The polymerizable composition according to claim 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. The polymerizable composition according to any one of claims 1 to 3, further comprising (D) a filler. The polymerizable composition according to any one of claims 1 to 4, wherein components (A) to (C) are contained in a single container. The polymerizable composition according to any one of claims 1 to 4, wherein components (A) to (C) are separated into two or more containers. An adhesive or sealant comprising the polymerizable composition according to any one of claims 1 to 6. The adhesive or sealant described in claim 7, used to fix, adhere, or protect an optical sensor module or its constituent components. A cured product obtained by curing the polymerizable composition described in any one of claims 1 to 6, or the adhesive or sealant described in claim 7 or 8. A semiconductor device or electronic component comprising the cured product according to claim 9. The semiconductor device or electronic component according to claim 10, which is an optical sensor module.