WO2023223979A1 - ポリオキシアルキレン鎖を有する化合物及びアクリル系共重合体を含有する組成物 - Google Patents

ポリオキシアルキレン鎖を有する化合物及びアクリル系共重合体を含有する組成物 Download PDF

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WO2023223979A1
WO2023223979A1 PCT/JP2023/017982 JP2023017982W WO2023223979A1 WO 2023223979 A1 WO2023223979 A1 WO 2023223979A1 JP 2023017982 W JP2023017982 W JP 2023017982W WO 2023223979 A1 WO2023223979 A1 WO 2023223979A1
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meth
acrylate
group
mass
composition
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 古川
優希 中村
清人 増田
弘 横田
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Resonac Corp
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Resonac Corp
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Priority to EP23807581.6A priority Critical patent/EP4512837A4/en
Priority to US18/861,584 priority patent/US20250346702A1/en
Priority to CN202380037336.2A priority patent/CN119137173A/zh
Priority to KR1020247040867A priority patent/KR20250010640A/ko
Priority to JP2024521731A priority patent/JPWO2023223979A1/ja
Publication of WO2023223979A1 publication Critical patent/WO2023223979A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
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    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to a composition containing a compound having a polyoxyalkylene chain and an acrylic copolymer.
  • a thermally conductive material (sometimes called a heat dissipation material) called a thermal interface material (TIM) is a material provided between a heat source and a heat dissipation member such as a heat sink, and is used to reduce the thermal resistance between the heat source and the heat dissipation member. It reduces heat and promotes heat conduction from the heat source. Since the heat generated from the heat source is efficiently conducted to the cooling member via the TIM, the heat is easily radiated from the heat radiating member.
  • a thermally conductive material sometimes called a heat dissipation material
  • TIM thermal interface material
  • thermally conductive materials many liquid materials, also called thermally conductive greases or thermally conductive greases, are known.
  • thermally conductive grease is used, a pump-out phenomenon may occur in which the grease is pushed out from between the members due to dripping after application or deformation of the member to which the thermally conductive grease is applied.
  • a thermally conductive material formed into a solid shape such as a sheet may be used.
  • a solid thermally conductive material can be obtained, for example, by curing a composition containing a polymerizable compound in addition to a thermally conductive filler.
  • Patent Document 1 discloses that it was discovered that a cured product of a curable composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups has excellent elongation, and that this curable composition It is stated that it has been found that it can be suitably used as a thermally conductive material by containing a thermally conductive filler.
  • One aspect of the present invention is a composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups, which is capable of forming a cured product with excellent breaking strength.
  • the purpose of this invention is to provide a composition with a unique composition.
  • a compound represented by the following formula (1) [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain. ]
  • a composition comprising: A composition in which the content of methyl (meth)acrylate is 25% by mass or more based on the total amount of monomer units contained in the copolymer.
  • the composition according to [1] further containing a thermally conductive filler.
  • a composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups forms a cured product with excellent breaking strength. It is possible to provide a composition that allows
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of an article.
  • FIG. 7 is a schematic cross-sectional view showing another embodiment of the article.
  • (meth)acryloyl means “acryloyl” and its corresponding “methacryloyl”, and the same applies to similar expressions such as “(meth)acrylate” and “(meth)acrylic”. .
  • the weight average molecular weight (Mw) and the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) in this specification are measured using gel permeation chromatography (GPC) under the following conditions, using polystyrene as a standard material. means the value determined as .
  • GPC gel permeation chromatography
  • a composition according to one embodiment of the present invention contains a compound represented by the following formula (1).
  • R 11 and R 12 each independently represent a hydrogen atom or a methyl group
  • R 13 represents a divalent group having a polyoxyalkylene chain.
  • R 11 and R 12 may be a hydrogen atom, and the other may be a methyl group. In another embodiment, both R 11 and R 12 may be hydrogen atoms. In another embodiment, both R 11 and R 12 may be methyl groups.
  • the polyoxyalkylene chain includes a structural unit represented by the following formula (1a).
  • R 13 may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by formula (1-2) below (polyethylene glycol di (meth)acrylate).
  • formula (1-2) polyethylene glycol di (meth)acrylate
  • R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and m is an integer of 2 or more.
  • the polyoxyalkylene chain includes a structural unit represented by the following formula (1b). This allows the composition to be easily handled.
  • R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di (meth)acrylate).
  • formula (1-3) polypropylene glycol di (meth)acrylate.
  • R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), respectively, and n is an integer of 2 or more.
  • the polyoxyalkylene chain preferably has the formula (1) described above, from the viewpoint of achieving both the strength of the cured product of the compound represented by formula (1) and the ease of handling of the composition. It is a copolymer chain containing a structural unit represented by (1a) and a structural unit represented by formula (1b).
  • the copolymer chain may be an alternating copolymer chain, a block copolymer chain, or a random copolymer chain.
  • the copolymer chain is preferably a random copolymer chain from the viewpoint of further lowering the crystallinity of the compound represented by formula (1) and making the composition easier to handle.
  • the polyoxyalkylene chain includes an oxytetramethylene group, an oxybutylene group, an oxypentylene group, in addition to the structural unit represented by formula (1a) and the structural unit represented by formula (1b). It may have an oxyalkylene group having 4 to 5 carbon atoms as a structural unit.
  • R 13 may be a divalent group further having another organic group.
  • the other organic group may be a chain group other than a polyoxyalkylene chain, such as a methylene chain (a chain containing -CH 2 - as a structural unit), a polyester chain (a chain containing -COO- in the structural unit), and a polyester chain (a chain containing -COO- in the structural unit). chain), polyurethane chain (chain containing -OCON- in the structural unit), etc.
  • the compound represented by formula (1) may be a compound represented by formula (1-4) below.
  • R 11 and R 12 have the same meanings as R 11 and R 12 in formula (1), and R 14 and R 15 each independently represent an alkylene group having 2 to 5 carbon atoms.
  • k1, k2 and k3 are each independently an integer of 2 or more.
  • k2 may be an integer of 16 or less, for example.
  • a plurality of R 14 and R 15 may be the same or different from each other.
  • the plurality of R 14 and R 15 preferably include an ethylene group and a propylene group, respectively. That is, the polyoxyalkylene chain represented by (R 14 O) k1 and the polyoxyalkylene chain represented by (R 15 O) k3 are each preferably an oxyethylene group (represented by the above formula (1a)). It is a copolymer chain containing a structural unit represented by the above formula (1b)) and an oxypropylene group (a structural unit represented by the above formula (1b)).
  • the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 100 or more.
  • the main chain of the compound represented by formula (1) becomes longer, resulting in even better elongation of the cured product and further increasing the strength of the cured product. be able to.
  • the number of oxyalkylene groups corresponds to m in formula (1-2), n in formula (1-3), and k1 and k3 in formula (1-4), respectively.
  • the number of oxyalkylene groups in the polyoxyalkylene chain is more preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more.
  • the number of oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.
  • the weight average molecular weight of the compound represented by formula (1) is preferably 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 9,000 or more, 10,000 or more, 11,000 or more, from the viewpoint that the cured product has lower elasticity and excellent elongation. 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more.
  • the weight average molecular weight of the compound represented by formula (1) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less, from the viewpoint of easily adjusting the viscosity of the composition. .
  • the compound represented by formula (1) may be liquid at 25°C.
  • the viscosity at 25° C. of the compound represented by formula (1) is preferably from the viewpoint of making it easier to apply the composition to the coating surface and increasing the adhesion of the cured product to the coating surface. , 1000 Pa.s or less, 800 Pa.s or less, 600 Pa.s or less, 500 Pa.s or less, 350 Pa.s or less, 300 Pa.s or less, or 200 Pa.s or less.
  • the viscosity at 25°C of the compound represented by formula (1) is 0.1 Pa.s or more, 0.2 Pa.s or more, 0.3 Pa.s or more, 1 Pa.s or more, 2 Pa.s or more, or 3 Pa.s or more. It may be greater than or equal to s.
  • the compound represented by formula (1) may be solid at 25°C.
  • the compound represented by formula (1) is preferably in a liquid state at 50°C.
  • the viscosity of the compound represented by formula (1) at 50° C. is preferably 100 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or less, even more preferably is 30 Pa ⁇ s or less, particularly preferably 20 Pa ⁇ s or less.
  • the viscosity of the compound represented by formula (1) at 50° C. may be 0.1 Pa ⁇ s or more, 0.2 Pa ⁇ s or more, or 0.3 Pa ⁇ s or more.
  • viscosity means a value measured based on JIS Z8803, specifically, a value measured with an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.) means.
  • E-type viscometer for example, PE-80L manufactured by Toki Sangyo Co., Ltd.
  • the viscosity of the compound represented by formula (1) can be adjusted by adjusting the weight average molecular weight of the compound.
  • the content of the compound represented by formula (1) is preferably 1% by mass or more, 1.2% by mass or more, or 1.3% by mass, based on the total amount of the composition, from the viewpoint that the cured product has better elongation. For example, it may be 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less.
  • the composition contains a compound represented by formula (1) as a polymerizable compound, and in one embodiment may further contain a compound represented by formula (2), and a compound represented by formula (3). It may further contain a compound represented by formula (1), a compound represented by formula (2), and a polymerizable compound other than the compound represented by formula (3). (Details will be described later).
  • the content of the compound represented by formula (1) is determined from the viewpoint that the cured product has better elongation.
  • total content of polymerizable components 7 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more, for example, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less. It may be.
  • composition according to one embodiment of the present invention contains, in addition to the compound represented by formula (1), methyl (meth)acrylate and an alkyl (meth)acrylate (hereinafter referred to as , "C2-C12 alkyl (meth)acrylate”) as a monomer unit (hereinafter also referred to as "acrylic copolymer”).
  • the content of methyl (meth)acrylate contained in the acrylic copolymer is 25% by mass or more based on the total amount of monomer units contained in the acrylic copolymer (hereinafter also simply referred to as "total amount of monomer units"). .
  • the content of methyl (meth)acrylate may be 27% by mass or more, 30% by mass or more, or 35% by mass or more, and 70% by mass or less, 60% by mass or less, 50% by mass, based on the total amount of monomer units. % or less, or 45% by mass or less.
  • the number of carbon atoms in the alkyl group in the C2-C12 alkyl (meth)acrylate may be 3 or more, 8 or less, 7 or less, or 6 or less.
  • the alkyl group may be linear, branched, or cyclic.
  • alkyl group in C2-C12 alkyl (meth)acrylate is linear
  • alkyl group in C2-C12 alkyl (meth)acrylate is linear
  • ethyl (meth)acrylate n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl ( meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, octyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate , and lauryl (meth)acrylate.
  • alkyl group in the C2-C12 alkyl (meth)acrylate is branched include isopropyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, and isobutyl (meth)acrylate. , isopentyl (meth)acrylate, isohexyl (meth)acrylate, isoheptyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and isodecyl (meth)acrylate. .
  • a specific example of the case where the alkyl group in the C2-C12 alkyl (meth)acrylate is cyclic (cycloalkyl group) is cyclohexyl (meth)acrylate.
  • C2-C12 alkyl (meth)acrylates may be used alone or in combination of two or more.
  • the content of C2-C12 alkyl (meth)acrylate contained in the acrylic copolymer is 40% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of monomer units. It may be 75% by weight or less, 70% by weight or less, or 65% by weight or less.
  • the acrylic copolymer may contain only methyl (meth)acrylate and C2-C12 alkyl (meth)acrylate as monomer units, and can be copolymerized with methyl (meth)acrylate and C2-C12 alkyl (meth)acrylate. It may further contain other monomer units. Examples of other monomer units include carboxyl group-containing monomers, hydroxyl group-containing monomers, isocyanate group-containing monomers, amino group-containing monomers, and epoxy group-containing monomers.
  • carboxyl group-containing monomers examples include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like.
  • Hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate. Examples include acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and the like.
  • Examples of monomers containing isocyanate groups include 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate.
  • Examples of amino group-containing monomers include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate. ) acrylate, etc.
  • Epoxy group-containing monomers include glycidyl (meth)acrylate, ⁇ -ethyl (meth)glycidyl acrylate, ⁇ -n-propyl (meth)glycidyl acrylate, ⁇ -n-butyl (meth)glycidyl acrylate, ) 3,4-epoxybutyl acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, ⁇ -ethyl (meth)acrylate-6,7- Epoxyheptyl, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6 (meth)acrylate -epoxyhexyl, ⁇ -methylglycidyl (meth)acrylate, ⁇ -methylglycidyl ⁇ -ethyl (meth)acrylate,
  • the content of other monomer units may be 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less, based on the total amount of monomer units.
  • Acrylic copolymers are alternating, block, or random copolymers containing methyl (meth)acrylate units, C2-C12 alkyl (meth)acrylate units, and optionally other monomer units. It may be a polymer, preferably a block copolymer.
  • the block copolymer consists of a block containing methyl (meth)acrylate units (hereinafter also referred to as "first block”) and a block containing C2-C12 alkyl (meth)acrylate (hereinafter referred to as "second block”). ).
  • the content of methyl (meth)acrylate contained in the first block may be 90% by mass or more, 95% by mass or more, or 99% by mass or more based on the total amount of monomer units contained in the first block.
  • the first block may be, for example, a polymethyl (meth)acrylate block containing only methyl (meth)acrylate as monomer units.
  • the content of C2-C12 alkyl (meth)acrylate contained in the second block is 90% by mass or more, 95% by mass or more, or 99% by mass or more based on the total amount of monomer units contained in the second block. It's good to be there.
  • the second block may contain one kind selected from C2-C12 alkyl (meth)acrylate, or two or more kinds, as a monomer unit.
  • the second block may be, for example, a poly n-butyl (meth)acrylate block containing only n-butyl (meth)acrylate as monomer units.
  • the block copolymer may be a diblock copolymer in which a first block and a second block are bonded in this order, and the first block, second block, and first block are bonded in this order.
  • a triblock copolymer bonded in sequence may also be used.
  • the content of the acrylic copolymer may be 0.05% by mass or more, 0.1% by mass or more, or 0.15% by mass or more, and 1% by mass or less, 0.05% by mass or more, based on the total amount of the composition. It may be 5% by mass or less, or 0.3% by mass or less.
  • the content of the acrylic copolymer may be 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more, and 10 parts by mass or less, based on 100 parts by mass of the total content of the polymerizable components. It may be 7 parts by mass or less, or 5 parts by mass or less.
  • the content of the acrylic copolymer is 5 parts by mass or more, 7 parts by mass or more, 10 parts by mass or more, or 13 parts by mass or more with respect to 100 parts by mass of the compound represented by formula (1).
  • the amount may be 40 parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less.
  • the composition may further contain a thixotropic agent.
  • the thixo-imparting agent is preferably an ester-based thixo-imparting agent containing an ester compound.
  • the thixotropic agent may be liquid at 25°C.
  • the ester-based thixotropic agent may contain at least one selected from the group consisting of phosphoric acid esters, fatty acid esters, and aromatic esters.
  • the phosphoric acid ester may be a polyether phosphoric acid ester.
  • polyether phosphoric acid esters include, for example, esters of polyoxyethylene alkyl ether phosphoric acid, esters of polyoxyethylene alkyl phenyl ether phosphoric acid, and esters of higher alcohol phosphoric acid.
  • ester-based thixotropic agents include Disparon 3500 (manufactured by Kusumoto Kasei Co., Ltd.), Fluonon RCM-100 (manufactured by Kyoeisha Kagaku Co., Ltd.), and BYK-R606 (manufactured by BYK-Chemie Japan Co., Ltd.). It will be done.
  • thixotropic agents preferably ester-based thixotropic agents
  • thixotropic agents may be used alone or in combination of two or more.
  • the content of the thixo-imparting agent may be 0.01% by mass or more, 0.02% by mass or more, or 0.03% by mass or more, based on the total amount of the composition. It may be 0.5% by weight or less, 0.3% by weight or less, or 0.1% by weight or less.
  • the content of the thixo-imparting agent is 0.1 parts by mass or more, 0.3 parts by mass or more, or 0.5 parts by mass with respect to the total 100 parts by mass of the content of the polymerizable components.
  • the amount may be greater than or equal to 5 parts by weight, less than 4 parts by weight, or less than 3 parts by weight.
  • the content of the thixo-imparting agent is 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass with respect to 100 parts by mass of the compound represented by formula (1). or more, and may be 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less.
  • the composition may further contain a compound represented by the following formula (2).
  • R 21 and R 22 each independently represent a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring.
  • R 23 represents a hydrogen atom or a methyl group.
  • one of R 21 and R 22 may be a hydrogen atom, and the other may be a monovalent organic group. In another embodiment, both R 21 and R 22 may be hydrogen atoms. In another embodiment, both R 21 and R 22 may be monovalent organic groups that may be bonded to each other to form a ring.
  • the monovalent organic group may be, for example, a monovalent hydrocarbon group or an alkyl group.
  • the number of carbon atoms in the monovalent hydrocarbon group (eg, alkyl group) may be, for example, 1 or more and 6 or less.
  • the alkyl group include methyl group, ethyl group, n-propyl group, and isopropyl group.
  • Examples of the compound represented by formula (2) in which R 21 and R 22 do not combine with each other to form a ring include dimethylacrylamide, diethylacrylamide, and diisopropylacrylamide.
  • R 21 and R 22 are preferably bonded to each other to form a ring.
  • the ring may be, for example, a 5-membered ring, a 6-membered ring, or a 7-membered ring, preferably a 6-membered ring.
  • the ring is formed by the nitrogen atom in formula (2) and the groups represented by R 21 and R 22 .
  • the ring may contain carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, etc. in addition to the nitrogen atom, and preferably contains only carbon atoms, hydrogen atoms, and oxygen atoms in addition to the nitrogen atom. .
  • the group represented by R 21 and R 22 may be a group containing a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, etc., and preferably a group containing only a carbon atom, a hydrogen atom, and an oxygen atom. It's good.
  • Examples of compounds represented by formula (2) in which R 21 and R 22 combine with each other to form a ring include N-(meth)acryloylmorpholine, N-acryloylthiomorpholine, and N-acryloyloxazoline. , N-acryloylthiazolidine, N-acryloyl imidazolidine, N-(meth)acryloylpiperazine, N-vinylpyrrolidone, and N-vinylcaprolactam.
  • the content of the compound represented by formula (2) is preferably 0.1% by mass or more, 0.2% by mass or more, 0.0% by mass or more, based on the total amount of the composition. .3% by weight or more, or 0.5% by weight or more, for example, 2% by weight or less, 1.5% by weight or less, 1.3% by weight or less, or 1% by weight or less.
  • the content of the compound represented by formula (2) is preferably 1 part by mass or more and 2 parts by mass with respect to a total of 100 parts by mass of the content of the polymerizable components, from the viewpoint that the cured product has better heat resistance. parts or more, 5 parts by mass or more, 8 parts by mass or more, or 9 parts by mass or more, for example, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, or 12 parts by mass or less. It's fine.
  • the composition may further contain a compound represented by the following formula (3).
  • R 31 and R 32 each independently represent a hydrogen atom or a methyl group
  • R 33 represents a divalent group having a poly(meth)acrylate chain.
  • one of R 31 and R 32 may be a hydrogen atom, and the other may be a methyl group. In another embodiment, both R 31 and R 32 may be hydrogen atoms. In another embodiment, both R 31 and R 32 may be methyl groups.
  • the poly(meth)acrylate chain includes a structural unit represented by the following formula (3a).
  • R 34 represents a hydrogen atom or a monovalent organic group
  • R 35 represents a hydrogen atom or a methyl group.
  • the monovalent organic group represented by R 34 may be, for example, a hydrocarbon group, or an organic group having an oxygen atom, a nitrogen atom, or the like.
  • the hydrocarbon group may be chain-like and may have a ring (for example, an aromatic ring).
  • the number of carbon atoms in the hydrocarbon group may be, for example, 1 or more and 18 or less.
  • Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group.
  • n-octyl group 2-ethylhexyl group, 2-propylheptyl group, nonyl group, decyl group, isodecyl group, dodecyl group, octadecyl group, phenyl group, tolyl group, and benzyl group.
  • Examples of the organic group having an oxygen atom include a group having an alkoxy group, a group having a hydroxyl group, a group having a carboxyl group, and a group having a glycidyl group.
  • Examples of groups having an alkoxy group include 2-methoxyethyl group and 3-methoxybutyl group.
  • Examples of groups having a hydroxyl group include 2-hydroxyethyl group, 2-hydroxypropyl group, and 4-hydroxybutyl group.
  • An example of a group having a carboxyl group is a carboxyl group.
  • An example of a group having a glycidyl group is a glycidyl group.
  • organic groups having an oxygen atom examples include 2-methoxyethyl group, 3-methoxybutyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, carboxyl group, and glycidyl group. Can be mentioned.
  • Examples of the organic group having a nitrogen atom include a group having an amino group or a nitrile group.
  • An example of a group having an amino group is a 2-aminoethyl group.
  • An example of a group having a nitrile group is a nitrile group. That is, examples of the organic group having a nitrogen atom include a 2-aminoethyl group and a nitrile group.
  • the monovalent organic group represented by R 34 may be a group having a polar group, and may be a group having a hydroxyl group or a carboxyl group.
  • the compound represented by formula (3) may be a compound represented by formula (3-2) below.
  • R 31 and R 32 have the same meanings as R 31 and R 32 in formula (3), respectively
  • R 34 and R 35 have the same meanings as R 34 and R 35 in formula (3a), respectively.
  • Yes, and a is an integer of 2 or more.
  • the weight average molecular weight of the compound represented by formula (3) is preferably 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, 10000 or more, 11000 or more, 12000 or more, or 13000 or more. That's all.
  • the weight average molecular weight of the compound represented by formula (3) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 34,000 or less, 31,000 or less, or 28,000 or less, from the viewpoint of easily adjusting the viscosity of the composition.
  • a in formula (3a) may be an integer such that the weight average molecular weight of the compound represented by formula (3) falls within the above range.
  • the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the compound represented by formula (3) is preferably 1.4 or less or 1.2 or less.
  • the compound represented by formula (3) may be liquid at 23°C.
  • the viscosity at 23°C of the compound represented by formula (3) is 1000 Pa. s or less, 800 Pa.s or less, 700 Pa.s or less, 600 Pa.s or less, or 550 Pa.s or less.
  • the viscosity at 25°C of the compound represented by formula (3) is 5 Pa ⁇ s or more, 10 Pa ⁇ s or more, 15 Pa ⁇ s or more, 20 Pa ⁇ s or more, 25 Pa ⁇ s or more, 30 Pa ⁇ s or more, or 35 Pa ⁇ s It may be more than that.
  • the glass transition temperature (Tg) of the compound represented by formula (3) may be 0°C or lower, -10°C or lower, or -30°C or lower, and may be -60°C or higher, -50°C or higher, or -40°C or lower. The temperature may be higher than °C. Glass transition temperature means a value measured by differential scanning calorimetry.
  • the content of the compound represented by formula (3) is preferably 0.1% by mass or more, 0.3% by mass or more, or It is 0.4% by mass or more, and may be, for example, 3% by mass or less, 2% by mass or less, or 1% by mass or less.
  • the content of the compound represented by formula (3) is preferably 1 part by mass or more and 3 parts by mass based on the total content of the polymerizable components of 100 parts by mass, from the viewpoint that the cured product has better heat resistance. parts or more, 5 parts by mass or more, or 6 parts by mass or more, and may be, for example, 40 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.
  • the composition may contain a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3) for the purpose of adjusting the physical properties of the composition. It may further contain other polymerizable compounds.
  • the other polymerizable compound may be, for example, a compound having one (meth)acryloyl group other than the compound represented by formula (2).
  • the compound may be, for example, an alkyl (meth)acrylate.
  • Other polymerizable compounds include, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a silane group, It may be a compound having a group containing a siloxane bond, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group.
  • the viscosity of the composition can be easily adjusted.
  • the composition contains a compound having a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in addition to the (meth)acryloyl group, the adhesion of the composition and its cured product to the member is further improved. can.
  • the alkyl group (the alkyl group moiety other than the (meth)acryloyl group) in the alkyl (meth)acrylate may be linear, branched, or cyclic.
  • the alkyl group may have, for example, 1 to 30 carbon atoms.
  • the number of carbon atoms in the alkyl group may be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 It may be between 14 and 14.
  • alkyl (meth)acrylates having a linear alkyl group examples include alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms, and linear alkyl groups having 12 to 30 carbon atoms. Examples include alkyl (meth)acrylates having the following.
  • alkyl (meth)acrylates having a linear alkyl group having 1 to 11 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. , n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, or undecyl (meth)acrylate.
  • Alkyl (meth)acrylates having a linear alkyl group having 12 to 30 carbon atoms include dodecyl (meth)acrylate (lauryl (meth)acrylate), tetradecyl (meth)acrylate, hexadecyl (meth)acrylate (cetyl (meth)acrylate), acrylate), octadecyl (meth)acrylate (stearyl (meth)acrylate), docosyl (meth)acrylate (behenyl (meth)acrylate), tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, octacosyl (meth)acrylate, etc. .
  • alkyl (meth)acrylates having a branched alkyl group examples include alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms, and alkyl having a branched alkyl group having 12 to 30 carbon atoms. (Meth)acrylates are mentioned.
  • alkyl (meth)acrylates having a branched alkyl group having 1 to 11 carbon atoms examples include s-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, isoamyl ( Examples include meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isononyl(meth)acrylate, and isodecyl(meth)acrylate.
  • alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms examples include isomyristyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl ( Examples include meth)acrylate, isopentadecyl(meth)acrylate, isohexadecyl(meth)acrylate, isoheptadecyl(meth)acrylate, isostearyl(meth)acrylate, decyltetradecanyl(meth)acrylate, and the like.
  • alkyl (meth)acrylates having a cyclic alkyl group examples include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, terpene (meth)acrylate, Examples include dicyclopentanyl (meth)acrylate.
  • Examples of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate and the like.
  • Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, Examples include polybutylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, and the like.
  • Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include tetrahydrofurfuryl (meth)acrylate.
  • Examples of the compound having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate.
  • Examples of the compound having a (meth)acryloyl group and a phenoxy group include phenoxyethyl (meth)acrylate.
  • Examples of compounds having a group containing a (meth)acryloyl group and a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyl Examples include triethoxysilane and 10-acryloyloxydecyltriethoxysilane.
  • Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate.
  • Examples of the compound having a (meth)acryloyl group and a halogen atom include (meth)acrylate having a fluorine atom.
  • Examples of (meth)acrylates having a fluorine atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 1,1,1,3,3,3-hexafluoro-2- Propyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, perfluoropentylmethyl (meth)acrylate, perfluorohexylmethyl (meth)acrylate , perfluoroheptylmethyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, perfluorononylmethyl (meth)acrylate, perfluorodecylmethyl (meth)
  • Examples of compounds having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylate, hydroxyalkylcycloalkane (meth)acrylate, and the like.
  • Examples of hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
  • Examples thereof include meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate, 10-hydroxydecyl(meth)acrylate, and 12-hydroxylauryl(meth)acrylate.
  • Examples of the hydroxyalkylcycloalkane (meth)acrylate include (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • Examples of compounds having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, and monohydroxyethyl phthalate acrylate (for example, Toagosei Co., Ltd.) Aronix M5400''), and 2-acryloyloxyethyl succinate (for example, ⁇ NK Ester A-SA'' manufactured by Shin Nakamura Chemical Co., Ltd.).
  • Examples of compounds having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. , N,N-diethylaminopropyl (meth)acrylate, and the like.
  • Examples of compounds having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, ⁇ -ethyl (meth)glycidyl acrylate, ⁇ -n-propyl (meth)glycidyl acrylate, ⁇ -n-butyl Glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, ⁇ -ethyl ( 6,7-epoxyheptyl meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, (meth)acrylic Examples include 5-methyl-5,6-epoxyhexyl acid, ⁇ -methylglycidyl (meth)acrylate, and ⁇ -methylglycidy
  • the content of the other polymerizable compounds is preferably 1% by mass or more and 2% by mass based on the total amount of the composition, from the viewpoint of making it easier to adjust the viscosity of the composition or increasing the adhesiveness of the composition. % or more, 3 mass % or more, or 3.5 mass % or more, and may be, for example, 10 mass % or less, 8 mass % or less, 6 mass % or less, or 5 mass % or less.
  • the content of the other polymerizable compounds is preferably determined based on 100 parts by mass of the total content of the polymerizable components, from the viewpoint of making it easier to adjust the viscosity of the composition or increasing the adhesion of the composition. , 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, or 60 parts by mass or more, for example, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 65 parts by mass. It may be the following.
  • the composition may further contain a polymerization initiator.
  • the polymerization initiator may be, for example, a thermal polymerization initiator that generates radicals by heat, a photopolymerization initiator that generates radicals by light, or the like.
  • the polymerization initiator is preferably a thermal polymerization initiator.
  • the composition contains a thermal polymerization initiator
  • a cured product of the composition can be obtained by applying heat to the composition.
  • the composition may be a composition that is cured by heating preferably at 105°C or higher, more preferably at 110°C or higher, even more preferably at 115°C or higher, for example, at 200°C or lower, at 190°C or lower, or The composition may be cured by heating at 180° C. or lower.
  • the heating time when heating the composition may be appropriately selected depending on the composition of the composition so that the composition is suitably cured.
  • thermal polymerization initiators include azo compounds and organic peroxides.
  • the azo compound include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl.
  • organic peroxides include benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di-t-butylperoxyhexahydroterephthalate, and t-butylperoxy-2.
  • Thermal polymerization initiators may be used alone or in combination of two or more.
  • a cured product of the composition is obtained by irradiating the composition with light (for example, light including at least a part of the wavelength of 200 to 400 nm (ultraviolet light)).
  • light for example, light including at least a part of the wavelength of 200 to 400 nm (ultraviolet light)
  • the conditions for light irradiation may be appropriately set depending on the type of photopolymerization initiator.
  • photopolymerization initiators include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime photopolymerization initiators. , a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, etc. .
  • benzoin ether photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one (for example, BASF Irgacure 651 (manufactured by Co., Ltd.), anisole methyl ether, and the like.
  • acetophenone photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone (for example, "Irgacure 184" manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2- hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (for example, “Irgacure 2959” manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1- (for example, "Irgacure 1173” manufactured by BASF), methoxyacetophenone, and the like.
  • 1-hydroxycyclohexyl phenyl ketone for example, "Irgacure 184" manufactured by BASF
  • 4-phenoxydichloroacetophenone 4-t-butyl-dichloroacetophenone
  • Examples of ⁇ -ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, etc. can be mentioned.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.
  • Examples of the benzoin-based photopolymerization initiator include benzoin.
  • Examples of the benzyl photopolymerization initiator include benzyl.
  • Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and ⁇ -hydroxycyclohexylphenyl ketone.
  • Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
  • thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2, Examples include 4-diisopropylthioxanthone and dodecylthioxanthone.
  • acylphosphine oxide photopolymerization initiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, and bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide.
  • the photopolymerization initiators described above may be used alone or in combination of two or more.
  • the content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, based on 100 parts by mass of the total content of polymerizable components, from the viewpoint of suitably proceeding the polymerization. , more preferably 0.1 part by mass or more, particularly preferably 0.5 part by mass or more.
  • the content of the polymerization initiator is determined based on the total content of the polymerizable components of 100 parts by mass, from the viewpoint of keeping the molecular weight of the polymer in the cured product of the composition within a suitable range and suppressing decomposition products. Preferably it is 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.
  • the composition may further contain a thermally conductive filler.
  • a thermally conductive filler is a filler having a thermal conductivity of 10 W/m ⁇ K or more.
  • the thermally conductive filler may be insulating or conductive.
  • the thermally conductive filler is preferably an insulating filler.
  • Materials constituting the insulating thermally conductive filler include aluminum oxide, aluminum hydroxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, silicon dioxide, aluminum fluoride, calcium fluoride, Examples include zinc oxide.
  • Examples of the material constituting the electrically conductive thermally conductive filler include aluminum, silver, copper, and the like.
  • the shape of the thermally conductive filler may be spherical or polyhedral.
  • the average particle size of the thermally conductive filler is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 30 ⁇ m or less, and 0.05 ⁇ m or more, 0.1 ⁇ m or more, from the viewpoint of being able to thinly arrange the cured product of the composition. , or 0.3 ⁇ m or more.
  • the average particle size of the thermally conductive filler means the particle size (D50) at which the volume cumulative particle size distribution is 50%, and is measured using a laser diffraction particle size distribution measuring device (for example, SALD-2300 (manufactured by Shimadzu Corporation)). It is measured using
  • the content of the thermally conductive filler is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass, based on the total amount of the composition. It may be 97% by mass or less, 95% by mass or less, or 93% by mass or less.
  • the content of the thermally conductive filler is preferably 65% by volume or more, more preferably 70% by volume or more, and even more preferably may be 75% by volume or more, and 90% by volume or less, 88% by volume or less, or 85% by volume or less.
  • the composition may further contain a coupling agent.
  • the coupling agent may be, for example, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.
  • the coupling agent is preferably a silane coupling agent.
  • the silane coupling agent may be a compound having an alkoxysilyl group such as a dialkoxysilyl group or a trialkoxysilyl group.
  • the silane coupling agent may have, for example, an organic functional group, an alkyl group having 1 to 10 carbon atoms, and the like. Examples of the organic functional group include a vinyl group, (meth)acryloyl group, epoxy group, amino group, mercapto group, and imidazole group.
  • the silane coupling agent preferably has a (meth)acryloyl group.
  • the above-mentioned coupling agents can be used alone or in combination of two or more.
  • the content of the coupling agent is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the thermally conductive filler content. It is 0.02 parts by mass or more, or 0.025 parts by mass or more. Moreover, the content of the coupling agent is preferably 2 parts by mass or less, 1.5 parts by mass or less, or 1 part by mass or less with respect to 100 parts by mass of the thermally conductive filler.
  • the coupling agent tends to self-condense, which may result in an excessive increase in the breaking strength of the cured product, an increase in the tensile modulus, and an excessive decrease in the elongation at break. This is because of their gender.
  • the coupling agent is chemically adsorbed on the surface of the thermally conductive filler.
  • the viscosity of the composition decreases and the breaking strength of the cured product of the composition becomes higher.
  • All of the coupling agents contained in the composition may be chemically adsorbed on the surface of the thermally conductive filler, or a portion may be chemically adsorbed on the surface of the thermally conductive filler.
  • the coupling agent is chemically adsorbed on the surface of the thermally conductive filler.
  • a solvent for example, methyl ethyl ketone
  • the thermally conductive filler is collected by filtration and vacuum dried.
  • drying is performed at less than 100°C.
  • the dried thermally conductive filler is added to excess methyl ethyl ketone (at least 40 times the mass of the thermally conductive filler contained in the composition), stirred, and left at room temperature (20 to 30°C) for 12 hours or more. After settling the thermally conductive filler, the supernatant liquid (90% by mass or more of the added methyl ethyl ketone) is removed. It is thought that this removes the coupling agent that has not been chemically adsorbed on the surface of the thermally conductive filler. Then, after drying the thermally conductive filler in an oven at 100° C., IR measurement (diffuse reflection method) of the thermally conductive filler is performed.
  • a coupling agent When a coupling agent is chemically adsorbed on the surface of a thermally conductive filler, a peak of a methoxy group, methyl group, or methylene chain derived from the coupling agent is observed in the range of 2800 to 3000 cm ⁇ 1 .
  • a liquid in which a coupling agent is hydrolyzed (hydrolyzed liquid) is prepared, and the hydrolyzed liquid is made to be thermally conductive.
  • hydrolyzed liquid examples include a method in which the thermally conductive filler is added to the filler, stirred, dried, and optionally crushed and classified.
  • the composition may further contain a tackifier.
  • tackifiers include rosin resins and terpene resins.
  • the content of the tackifier may be 0.1 parts by mass or more, 1 part by mass or more, or 3 parts by mass or more, and 20 parts by mass or less, 15 parts by mass or more, based on 100 parts by mass of the total content of the polymerizable components. It may be up to 12 parts by weight, or up to 10 parts by weight.
  • the composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of the cured product of the composition.
  • the antioxidant may be, for example, a phenolic antioxidant, a benzophenone antioxidant, a benzoate antioxidant, a hindered amine antioxidant, a benzotriazole antioxidant, etc., and preferably a phenolic antioxidant. It is.
  • the phenolic antioxidant has, for example, a hindered phenol structure (hindered phenol ring).
  • the hindered phenol structure may be, for example, a structure in which a t-butyl group is bonded to one or both positions ortho to the hydroxyl group in the phenol ring.
  • the phenolic antioxidant has, for example, one or more such hindered phenol rings, preferably two or more, more preferably three or more, still more preferably four or more.
  • the content of the antioxidant may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and 10% by mass or less, 9% by mass or less, based on the total amount of the composition. It may be 8% by mass or less, or 7% by mass or less.
  • the composition can further contain other additives as necessary.
  • Other additives include, for example, surface treatment agents (excluding coupling agents), dispersants, hardening accelerators, colorants, crystal nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration damping agents, and dehydrating agents. , flame retardant aids (eg, metal oxides), and the like.
  • the content of other additives may be 0.1% by mass or more and 30% by mass or less based on the total amount of the composition.
  • the composition is preferably liquid at 25°C. Thereby, it is possible to suitably apply the coating material to the surface of an object such as a member serving as a heat source or a cooling member, and it is also possible to improve the adhesion to the coating surface.
  • the composition may be solid at 25°C. In that case, it is preferable that the composition becomes liquid by heating (for example, at 50° C. or higher).
  • composition set The above-mentioned composition may be in the form of a multi-component composition (composition set).
  • a composition set according to one embodiment includes a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. At least one of the first liquid and the second liquid contains the compound represented by the above-mentioned formula (1). Moreover, at least one of the first liquid and the second liquid contains the above-mentioned acrylic copolymer.
  • composition set according to the present embodiment by mixing the first liquid and the second liquid, a cured product of the mixture of the first liquid and the second liquid can be immediately obtained. That is, according to the composition set, a cured product of the composition can be obtained at a high speed.
  • the first liquid contains an oxidizing agent, a compound represented by formula (1), and an acrylic copolymer
  • the second liquid preferably contains a reducing agent, a compound represented by formula (1). Contains a compound and an acrylic copolymer.
  • Content of the compound represented by formula (1) based on the total amount of liquids constituting the composition set may be the same as the content range of the compound represented by formula (1) based on the total amount of the composition described above. The same applies to the content of the acrylic copolymer contained in the composition set.
  • the oxidizing agent contained in the first liquid has a role as a polymerization initiator (radical polymerization initiator).
  • the oxidizing agent may be, for example, an organic peroxide or an azo compound.
  • Organic peroxides may be, for example, hydroperoxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, diacyl peroxides, and the like.
  • the azo compound may be AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile), and the like.
  • One type of oxidizing agent can be used alone or two or more types can be used in combination.
  • hydroperoxide examples include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
  • peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, and di-2-ethoxymethoxyperoxydicarbonate.
  • Peroxy esters include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t -hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di( 2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanonate, t-hexylperoxy-2-ethylhexanonate, t-butylperoxy-2 -Ethylhexanonate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclo
  • Peroxyketals include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1- Bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 2,2-bis(t-butylperoxy)decane, etc. Can be mentioned.
  • dialkyl peroxide examples include ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t- Examples include butylcumyl peroxide.
  • diacyl peroxide examples include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and succinic peroxide. , benzoyl peroxytoluene, benzoyl peroxide, and the like.
  • the oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, and even more preferably cumene hydroperoxide.
  • the content of the oxidizing agent may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and 10% by mass or less, 5% by mass, based on the total amount of liquid constituting the composition set. % or less, or 3% by mass or less.
  • the reducing agent contained in the second liquid may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt, or the like.
  • a tertiary amine include triethylamine, tripropylamine, tributylamine, N,N-dimethylparatoluidine, and the like.
  • thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea.
  • transition metal salts include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, and the like.
  • One type of reducing agent can be used alone or two or more types can be used in combination.
  • the reducing agent is preferably a thiourea derivative or a transition metal salt from the viewpoint of excellent curing speed.
  • the thiourea derivative may be, for example, ethylenethiourea.
  • the transition metal salt is preferably vanadyl acetylacetonate.
  • the content of the reducing agent may be 0.05% by mass or more, 0.1% by mass or more, or 0.3% by mass or more, and 5% by mass or less, based on the total amount of liquid constituting the composition set. It may be 3% by mass or less, or 1% by mass or less.
  • the composition set further includes an ester-based thixo-imparting agent, a compound represented by formula (2), a compound represented by formula (3), other polymerizable compounds, and additives that can be used in the above-mentioned composition. May be contained.
  • additives that may be used in the compositions described above include coupling agents, tackifiers, antioxidants, and other additives.
  • the composition set may further contain a thermally conductive filler that can be used in the above-described composition, and a coupling agent may be chemically adsorbed on the surface of the thermally conductive filler.
  • These components may be contained in one or both of the first liquid and the second liquid, or may be contained in a third liquid different from the first liquid and the second liquid. The content of these components based on the total amount of liquid constituting the composition set may be the same as the range of the content of these components based on the total amount of the composition described above.
  • compositions and composition sets have thermal conductivity and excellent breaking strength. Suitable for applications such as battery binders, stress relievers, sealants, coating agents, and paints. Similarly, cured products of the above-mentioned compositions and cured products of mixtures of composition sets have excellent breaking strength and are therefore suitable for each of the above-mentioned uses.
  • the composition and composition set contain a thermally conductive filler
  • the composition, composition set, and cured product thereof are particularly suitably used as a thermally conductive material (also called a heat dissipation material).
  • the coupling agent is chemically adsorbed on the surface of the thermally conductive filler, the composition and composition set have a low viscosity and their cured products have higher breaking strength, making it especially suitable for the above applications. suitable.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of an electronic component including a cured product.
  • the electronic component 1A shown in FIG. 1 includes a semiconductor chip 21 as a heat source and a heat sink 22 as a heat radiation section.
  • the electronic component 1A includes a cured product 11 provided between a semiconductor chip 21 and a heat sink 22.
  • the cured product 11 is a cured product of the above-mentioned composition or a cured product of a mixture of composition sets.
  • the cured product 11 Since the cured product 11 has thermal conductivity, the cured product 11 acts as a thermally conductive material (thermal interface material) in the electronic component 1A, and heat is conducted from the semiconductor chip 21 to the heat sink 22. Heat is then radiated from the heat sink 22 to the outside.
  • thermally conductive material thermal interface material
  • the cured product 11 Since the cured product 11 has excellent heat resistance, deterioration of the cured product 11 due to heat is suppressed. Therefore, heat generated from the semiconductor chip 21 can be effectively conducted to the heat sink 22.
  • the cured product 11 can also be obtained by placing a liquid composition (or composition set) between the semiconductor chip 21 and the heat sink 22 and then curing it. Therefore, the generation of voids due to dripping and pump-out phenomena can be suppressed, and as a result, the adhesiveness of the cured product 11 (adhesion to the surfaces of the semiconductor chip 21 and the heat sink 22) can be made excellent. .
  • the curing means and curing conditions of the composition may be adjusted depending on the composition of the composition or the type of polymerization initiator.
  • the cured product 11 is placed in direct contact with the semiconductor chip 21 and the heat sink 22, but the cured product 11 only needs to be in thermal contact with the heat source, and other In embodiments, it may be placed in contact with a heat source (for example, a semiconductor chip) via another member.
  • a heat source for example, a semiconductor chip
  • FIG. 2 is a schematic cross-sectional view showing another embodiment of an electronic component including a cured product.
  • the electronic component 1B shown in FIG. 2 includes a semiconductor chip 21 as a heat source arranged on one surface of a substrate 23 with an underfill 24 interposed therebetween, a heat sink 22 as a heat dissipation part, and a space between the semiconductor chip 21 and the heat sink 22.
  • the processor is equipped with a heat spreader 25 provided therein.
  • a first cured material 11 is provided between the semiconductor chip 21 and the heat spreader 25 so as to be in contact with the semiconductor chip 21 .
  • a second cured product 11 is provided between the heat spreader 25 and the heat sink 22.
  • the substrate 23, underfill 24, and heat spreader 25 may be formed of materials commonly used in the technical field.
  • the substrate 23 may be a laminate substrate or the like
  • the underfill 24 may be made of resin such as epoxy resin
  • the heat spreader 25 may be a metal plate or the like.
  • the first cured product 11 and the second cured product 11 are a cured product of the above-mentioned curable composition or a cured product of a mixture of the above-mentioned curable composition set.
  • the first cured product 11 is in direct contact with the semiconductor chip 21 which is a heat source, but the second cured product 11 is thermally applied to the semiconductor chip 21 which is a heat source via the first cured product 11 and the heat spreader 25. is in contact with
  • first cured product 11 and the second cured product 11 have thermal conductivity, they work as a thermally conductive material (thermal interface material) in the electronic component 1B. That is, the first cured product 11 promotes heat conduction from the semiconductor chip 21 to the heat spreader 25. Further, the second cured product 11 promotes heat conduction from the heat spreader 25 to the heat sink 22. Heat is then radiated from the heat sink 22 to the outside.
  • the first cured product 11 and the second cured product 11 also have excellent heat resistance, deterioration of the first cured product 11 and the second cured product 11 due to heat is suppressed. Therefore, the heat generated from the semiconductor chip 21 can be more effectively conducted to the heat spreader 25, and furthermore, the heat can be more effectively conducted to the heat sink 22.
  • the first cured product 11 and the second cured product 11 are obtained by placing a liquid composition (composition set) between the semiconductor chip 21 and the heat spreader 25 or between the heat spreader 25 and the heat sink 22, and then curing the composition. It can also be obtained by Therefore, also in the electronic component 1B, it is possible to suppress the generation of voids due to dripping of the composition (composition set) and pump-out phenomenon, and as a result, the formation of voids in the first cured product 11 and the second cured product 11 can be suppressed. Adhesion (adhesion to the surfaces of the semiconductor chip 21, heat spreader 25, and/or heat sink 22) can be made excellent.
  • (C) Compound represented by the following formula (3-3) ("RC200C” manufactured by Kaneka Corporation, weight average molecular weight: 18000, R 31 and R 32 in formula (3-3) are hydrogen atoms or methyl groups. and R 34 is a group having a polar group, viscosity at 23°C: 530 Pa s, Tg: -39°C)
  • D-1 2-ethylhexyl acrylate (“AEH” manufactured by Nippon Shokubai Co., Ltd.)
  • D-2) Isodecyl acrylate (“FA111A” manufactured by Showa Denko Materials Co., Ltd.)
  • D-3) 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • D-4) 2-acryloyloxyethyl succinate (“NK ester A-SA” manufactured by Shin Nakamura Kogyo Co., Ltd.)
  • E-1) Triblock copolymer in which polymethyl methacrylate block, poly n-butyl acrylate block, and polymethyl methacrylate block are bonded in this order (“Clarity (registered trademark) LA2270” manufactured by Kuraray Co., Ltd., total amount of monomer units) Content of methyl methacrylate based on: 40% by mass, weight average molecular weight: approximately 50,000)
  • E-2) Triblock copolymer in which polymethyl methacrylate block, poly n-butyl acrylate block, and polymethyl methacrylate block are bonded in this order (“Clarity (registered trademark) LA2250” manufactured by Kuraray Co., Ltd., total amount of monomer units) Content of methyl methacrylate based on: 30% by mass, weight average molecular weight: approximately 46,000)
  • e-1) Triblock copolymer in which polymethyl methacrylate block, poly n-butyl acrylate block, and polymethyl methacrylate block
  • Tackifier (“Tackifier KE311” manufactured by Arakawa Chemical Industry Co., Ltd.)
  • H Phenolic antioxidant (“Irganox1010” manufactured by BASF Japan Ltd.)
  • the mixed filler was surface treated with coupling agents (J-1) and (J-2) before being mixed with other components.
  • 0.025 parts by mass of coupling agent (J-1) and 0.025 parts by mass of coupling agent (J-2) were used with respect to 100 parts by mass of the mixed filler.
  • the specific method of surface treatment is as follows.
  • the above mixed filler was put into a 10L planetary mixer (the inner wall and stirring blades were made of stainless steel), and after stirring at a rotation speed of 200 rpm to 500 rpm for 10 minutes, a hydrolyzed solution of a coupling agent prepared by the method described below was added, The mixture was stirred for 10 minutes at a rotation speed of 200 rpm to 500 rpm. Thereafter, it was transferred to a vat, dried in an oven at 120° C. for 8 hours, and crushed and classified as necessary to obtain a thermally conductive filler after surface treatment.
  • the method for preparing the coupling agent hydrolysis treatment solution is as follows.
  • a 0.1 mol/L acetic acid aqueous solution, methanol, and a coupling agent (J-1) were blended in a beaker at a blending ratio of 38% by mass of acetic acid aqueous solution, 56% by mass of methanol, and 6% by mass of coupling agent.
  • the mixture was stirred and mixed at °C for 1 hour.
  • methanol and a coupling agent (J-2) were further blended, and the mixture was stirred and mixed at 25° C. for 10 minutes to prepare a hydrolyzed solution.
  • the hydrolyzed solution of the coupling agent was added to the mixed filler within 30 minutes after preparation.
  • the ratio of the volume of the mixed filler after surface treatment to the total volume of other components was 25:75.
  • (e-1) is used instead of (E-1) or (E-2)
  • turbidity occurs during the preparation of the composition, and the preparation of the composition and the cured product described below. It was not possible to create and evaluate the product.
  • the cured product was cut into squares of 10 mm x 10 mm x 0.2 mm, blackened with graphite spray, and then subjected to a xenon flash method (NETZSCH-Geratebau GmbH, "LFA447 nanoflash” manufactured by Selb/Bayern) at 25 °C.
  • the thermal diffusivity was measured. From the product of this value, the density measured by the Archimedes method, and the specific heat at 25°C measured with a differential scanning calorimeter (TA Instruments "DSC250”), the thickness of the cured product is determined based on the following formula.
  • the thermal conductivity in the direction was determined.
  • Table 1 shows the measurement results of each physical property for the compositions of Examples and Comparative Examples and their cured products.
  • 1A, 1B Electronic component, 11... Cured product of composition, 21... Semiconductor chip (heat source), 22... Heat sink, 23... Substrate, 24... Underfill, 25... Heat spreader.

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PCT/JP2023/017982 2022-05-19 2023-05-12 ポリオキシアルキレン鎖を有する化合物及びアクリル系共重合体を含有する組成物 Ceased WO2023223979A1 (ja)

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US18/861,584 US20250346702A1 (en) 2022-05-19 2023-05-12 Composition that contains compound having polyoxyalkylene chain and acrylic copolymer
CN202380037336.2A CN119137173A (zh) 2022-05-19 2023-05-12 含有具有聚氧亚烷基链的化合物及丙烯酸系共聚物的组合物
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Publication number Priority date Publication date Assignee Title
WO2011048802A1 (ja) * 2009-10-23 2011-04-28 クラレメディカル株式会社 重合性組成物及び歯科材料
JP2013203977A (ja) * 2012-03-29 2013-10-07 Dainippon Printing Co Ltd 粘着シートおよび非粘着シート
JP2018111796A (ja) * 2017-01-11 2018-07-19 アイカ工業株式会社 Ｌｅｄ硬化型防湿絶縁コート剤組成物
WO2021107001A1 (ja) 2019-11-29 2021-06-03 昭和電工マテリアルズ株式会社 硬化性組成物及び物品

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JP6338915B2 (ja) * 2014-04-07 2018-06-06 日本カーバイド工業株式会社 粘着剤組成物及び粘着シート
JP2021098772A (ja) * 2019-12-20 2021-07-01 東洋インキＳｃホールディングス株式会社 活性エネルギー線重合性組成物

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Publication number Priority date Publication date Assignee Title
WO2011048802A1 (ja) * 2009-10-23 2011-04-28 クラレメディカル株式会社 重合性組成物及び歯科材料
JP2013203977A (ja) * 2012-03-29 2013-10-07 Dainippon Printing Co Ltd 粘着シートおよび非粘着シート
JP2018111796A (ja) * 2017-01-11 2018-07-19 アイカ工業株式会社 Ｌｅｄ硬化型防湿絶縁コート剤組成物
WO2021107001A1 (ja) 2019-11-29 2021-06-03 昭和電工マテリアルズ株式会社 硬化性組成物及び物品

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Title
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