Classifications

• • 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
  • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/10—Metal compounds
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

• the present invention relates to a two-component resin composition. More specifically, the present invention relates to a two-component resin composition that is useful as a heat dissipation material, etc.
• heat dissipation material for example, a thermally conductive composition in which a metal filler is dispersed in a resin is known.
• Patent Document 1 discloses a two-component resin composition for heat dissipation materials containing liquid A and liquid B, in which liquid A contains a (meth)acrylic polymer, a radical polymerizable monomer, a reaction accelerator, and at least one crosslinking agent selected from the group consisting of a (meth)acrylate crosslinking agent and an allyl crosslinking agent, and liquid B contains a (meth)acrylic polymer and a peroxide polymerization initiator.
• liquid A contains a (meth)acrylic polymer, a radical polymerizable monomer, a reaction accelerator, and at least one crosslinking agent selected from the group consisting of a (meth)acrylate crosslinking agent and an allyl crosslinking agent
• liquid B contains a (meth)acrylic polymer and a peroxide polymerization initiator.
• the present invention was made in consideration of the above-mentioned current situation, and aims to provide a two-component resin composition that can achieve both an extended curing time and a high monomer conversion rate.
• the inventors conducted various studies on two-component resin compositions and found that a two-component resin composition consisting of a component A containing a polymerizable monomer and a reaction accelerator, in which the ratio of aromatic vinyl monomer in the polymerizable monomer is within a specified range, and a component B containing an initiator, can achieve both an extended curing time and a high monomer conversion rate. They came to the conclusion that this can neatly solve the above problems, and thus arrived at the present invention.
• the present invention includes the following two-component resin composition, etc.
• a two-component resin composition consisting of a liquid A and a liquid B, wherein the liquid A contains a polymerizable monomer and a reaction accelerator, the polymerizable monomer contains an aromatic vinyl monomer, and the content of the aromatic vinyl monomer is more than 0 mass% and 60 mass% or less relative to 100 mass% of the polymerizable monomer, and the liquid B contains an initiator.
• the polymerizable monomer comprises a monomer having a glass transition temperature of ⁇ 180 to ⁇ 20° C. when homopolymerized.
• the two-component resin composition of the present invention has the above-mentioned composition and can achieve both an extended curing time and a high monomer conversion rate, so it can be suitably used, for example, as a resin for heat dissipation materials, an adhesive, a pressure sensitive adhesive, etc.
• the two-part resin composition of the present invention is a two-part resin composition consisting of part A and part B.
• a cured product can be obtained by reacting part A with part B.
• the above-mentioned solution A contains a polymerizable monomer and a reaction accelerator, the polymerizable monomer contains an aromatic vinyl monomer, and the content of the aromatic vinyl monomer is more than 0 mass% and 60 mass% or less with respect to 100 mass% of the polymerizable monomer.
• the solution B is characterized by containing an initiator.
• the content ratio of the polymerizable monomer in the above-mentioned Solution A is not particularly limited, but when the Solution A does not contain inorganic particles, it is preferably 40 to 99.9% by mass relative to 100% by mass of the total amount of Solution A. It is more preferably 42 to 90% by mass, even more preferably 44 to 80% by mass, still more preferably 45 to 70% by mass, still more preferably 46 to 65% by mass, and particularly preferably 47 to 60% by mass.
• the content of the polymerizable monomer is preferably 40 to 99.9% by mass, more preferably 42 to 90% by mass, even more preferably 44 to 80% by mass, still more preferably 45 to 70% by mass, still more preferably 46 to 65% by mass, and particularly preferably 47 to 60% by mass, relative to 100% by mass of the total amount of Liquid A excluding the inorganic particles.
• the content of the polymerizable monomer is preferably 0.8 to 40% by mass, more preferably 1.0 to 30% by mass, even more preferably 1.5 to 20% by mass, and particularly preferably 2.0 to 12.0% by mass, relative to 100% by mass of the total amount of Solution A including the inorganic particles.
• the content of the aromatic vinyl monomer is preferably 1 to 60% by mass, more preferably 2 to 55% by mass, and even more preferably 4 to 50% by mass, relative to 100% by mass of the polymerizable monomer. In one aspect, the content of the aromatic vinyl monomer is 5 to 40% by mass, or 6 to 30% by mass, relative to 100% by mass of the polymerizable monomer, which is also one of the preferred embodiments of the present invention.
• the content of the reaction accelerator is not particularly limited, but when the solution A does not contain inorganic particles, the content is preferably 0.001 to 5 mass % relative to 100 mass % of the total amount of the solution A. More preferably, the content is 0.01 to 3 mass %, and further preferably, the content is 0.02 to 2 mass %.
• the content of the reaction accelerator is preferably 0.001 to 5 mass %, more preferably 0.01 to 3 mass %, and even more preferably 0.02 to 2 mass %, relative to 100 mass % of the total amount of Liquid A excluding the inorganic particles.
• the content of the reaction accelerator is preferably 0.00002 to 2% by mass, more preferably 0.0002 to 1% by mass, and even more preferably 0.001 to 0.3% by mass, based on 100% by mass of the total amount of Solution A including the inorganic particles.
• the mass of the metal compound in this specification is calculated in terms of the mass of the metal.
• the content of the reaction accelerator is preferably 0.001 to 10% by mass relative to 100% by mass of the polymerizable monomer. More preferably, it is 0.005 to 8% by mass, even more preferably, it is 0.01 to 6% by mass, and particularly preferably, it is 0.02 to 4% by mass.
• the content of the reaction accelerator is preferably 0.1 to 500% by mass relative to 100% by mass of the initiator in the B solution. More preferably, it is 0.2 to 250% by mass, even more preferably, it is 0.4 to 100% by mass, even more preferably, it is 0.5 to 80% by mass, even more preferably, it is 1 to 75% by mass, and particularly preferably, it is 1.5 to 70% by mass.
• the content is not particularly limited, but when the solution A does not contain inorganic particles, the content is preferably 0.001 to 2 mass % relative to 100 mass % of the total amount of the solution A. More preferably, the content is 0.01 to 1 mass %, and even more preferably, the content is 0.02 to 0.3 mass %.
• the content of the reaction accelerator is preferably 0.001 to 2 mass %, more preferably 0.01 to 1 mass %, and even more preferably 0.02 to 0.3 mass %, relative to 100 mass % of the total amount of Liquid A excluding the inorganic particles.
• the content of the reaction accelerator is preferably 0.0001 to 0.4% by mass, more preferably 0.001 to 0.2% by mass, and even more preferably 0.002 to 0.06% by mass, based on 100% by mass of the total amount of Solution A including the inorganic particles.
• the content is not particularly limited, but when the solution A does not contain inorganic particles, the content is preferably 0.01 to 5 mass % relative to 100 mass % of the total amount of the solution A. More preferably, the content is 0.05 to 4 mass %, and further preferably, the content is 0.1 to 3 mass %.
• the content of the reaction accelerator is preferably 0.01 to 5 mass %, more preferably 0.05 to 4 mass %, and even more preferably 0.1 to 3 mass %, relative to 100 mass % of the total amount of Liquid A excluding the inorganic particles.
• the content of the reaction accelerator is preferably 0.0001 to 1 mass %, more preferably 0.005 to 0.8 mass %, and even more preferably 0.01 to 0.6 mass %, based on 100 mass % of the total amount of Solution A including inorganic particles.
• the content is preferably 0.005 to 5 mass %, more preferably 0.01 to 3 mass %, further preferably 0.03 to 1 mass %, and particularly preferably 0.05 to 0.5 mass %, based on 100 mass % of the polymerizable monomer.
• the content is preferably 0.05 to 10 mass %, more preferably 0.1 to 8 mass %, further preferably 0.3 to 6 mass %, and particularly preferably 0.5 to 5 mass %, based on 100 mass % of the polymerizable monomer.
• the content is preferably 0.1 to 100 mass% relative to 100 mass% of the initiator in Solution B. More preferably, it is 0.2 to 60 mass%, still more preferably 0.4 to 40 mass%, still more preferably 0.6 to 20 mass%, still more preferably 0.8 to 15 mass%, and particularly preferably 1 to 10 mass%.
• the content is preferably 1 to 300% by mass relative to 100% by mass of the initiator in the solution B. More preferably, the content is 2 to 250% by mass, even more preferably, the content is 4 to 200% by mass, even more preferably, the content is 6 to 150% by mass, and particularly preferably, the content is 10 to 100% by mass.
• the content of the initiator is not particularly limited, but is preferably 1.5 to 50% by mass relative to 100% by mass of the polymerizable monomer, which allows the resin composition to be cured more sufficiently and allows the odor derived from the aromatic vinyl monomer to be more sufficiently suppressed.
• the content of the initiator is more preferably from 2 to 30% by mass, further preferably from 2.5 to 20% by mass, and particularly preferably from 3 to 12% by mass.
• the above-mentioned solution B preferably contains a reaction-accelerating auxiliary.
• the total ratio of the initiator, the reaction accelerator, and the reaction accelerator aid in the two-component resin composition is preferably 2 to 50% by mass, more preferably 4 to 30% by mass, and further preferably 6 to 25% by mass, based on 100% by mass of the polymerizable monomer.
• the total ratio of the reaction accelerator and reaction accelerator aid in the two-component resin composition is preferably 10 to 2000% by mass relative to 100% by mass of the initiator. It is more preferably 15 to 1000% by mass, even more preferably 20 to 500% by mass, even more preferably 50 to 400% by mass, and even more preferably 80 to 350% by mass.
• the total ratio of the initiator, the reaction accelerator using a metal compound, and the reaction accelerator aid in the two-component resin composition is preferably 2 to 50% by mass, more preferably 4 to 40% by mass, and even more preferably 5 to 30% by mass, based on 100% by mass of the polymerizable monomer.
• the total ratio of the initiator, the reaction accelerator other than the metal compound, and the reaction accelerator auxiliary in the two-component resin composition is preferably 2 to 50% by mass, more preferably 4 to 40% by mass, and further preferably 5 to 30% by mass, based on 100% by mass of the polymerizable monomer.
• the total ratio of the reaction accelerator using a metal compound and the reaction accelerator auxiliary in the two-component resin composition is preferably 10 to 2000% by mass, more preferably 15 to 1000% by mass, even more preferably 20 to 500% by mass, still more preferably 50 to 400% by mass, and even more preferably 100 to 350% by mass, relative to 100% by mass of the initiator.
• the total ratio of the reaction accelerator other than the metal compound and the reaction accelerator auxiliary in the two-component resin composition is preferably 10 to 2000% by mass, more preferably 15 to 1000% by mass, even more preferably 20 to 500% by mass, still more preferably 50 to 400% by mass, and even more preferably 100 to 350% by mass, relative to 100% by mass of the initiator.
• the reaction accelerator in the above-mentioned solution A preferably contains a metal compound.
• the ratio of the metal compound in the reaction accelerator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, and most preferably 100% by mass, based on 100% by mass of the reaction accelerator.
• the ratio of the metal compound in the reaction accelerator is preferably 1 to 100 mass %, more preferably 1 to 80 mass %, even more preferably 2 to 60 mass %, particularly preferably 4 to 50 mass %, and even more preferably 5 to 40 mass %, based on 100 mass % of the reaction accelerator.
• the reaction-accelerating assistant in the above-mentioned solution B preferably contains a diketone compound.
• the content ratio of the diketone compound is not particularly limited, but is preferably 1 to 600 mol, more preferably 5 to 400 mol, still more preferably 10 to 200 mol, and particularly preferably 12 to 50 mol, per 1 mol of the metal compound.
• the total ratio of the diketone compound and the metal in the metal compound in the two-component resin composition is preferably 10 to 2000% by mass relative to 100% by mass of the initiator. It is more preferably 15 to 1000% by mass, even more preferably 20 to 500% by mass, even more preferably 50 to 400% by mass, even more preferably 100 to 350% by mass, and particularly preferably 100 to 300% by mass.
• the total content of the diketone compound, the metal in the metal compound, and the initiator is preferably 2 to 50% by mass relative to 100% by mass of the polymerizable monomer. It is more preferably 4 to 40% by mass, even more preferably 5 to 30% by mass, and particularly preferably 6 to 25% by mass.
• the above-mentioned liquid A and/or liquid B preferably contain a (meth)acrylic polymer as described below.
• the content ratio of the (meth)acrylic polymer in the above-mentioned two-component resin composition is not particularly limited, but when the liquid A and the liquid B do not contain inorganic particles, it is preferably 0 to 60 mass% relative to 100 mass% of the two-component resin composition (total amount of liquid A and liquid B). It is more preferably 0 to 40 mass%, and even more preferably 10 to 30 mass%.
• the content of the (meth)acrylic polymer is preferably 0 to 60% by mass, more preferably 0 to 40% by mass, and even more preferably 10 to 30% by mass, relative to 100% by mass of the two-component resin composition (total amount of Liquid A and Liquid B) excluding the inorganic particles.
• the content of the (meth)acrylic polymer is preferably 0 to 24% by mass, more preferably 0 to 10% by mass, and even more preferably 0.5 to 4.5% by mass, relative to 100% by mass of the two-component resin composition containing inorganic particles (total amount of Liquid A and Liquid B).
• the content of the (meth)acrylic polymer in the two-component resin composition is preferably 0 to 150% by mass relative to 100% by mass of the polymerizable monomer. It is more preferably 25 to 120% by mass, and even more preferably 50 to 100% by mass.
• the above-mentioned liquid A and/or liquid B preferably contain a plasticizer as described below.
• the content ratio of the above-mentioned plasticizer is not particularly limited, but when the liquid A and liquid B do not contain inorganic particles, it is preferably 10 to 80 mass% with respect to 100 mass% of the two-component resin composition (total amount of liquid A and liquid B). It is more preferably 25 to 70 mass%, and even more preferably 40 to 60 mass%.
• the content of the plasticizer is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, and even more preferably 40 to 60% by mass, based on 100% by mass of the two-component resin composition excluding the inorganic particles (total amount of Liquid A and Liquid B).
• the content of the plasticizer is preferably 0.2 to 32% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass, based on 100% by mass of the two-component resin composition containing inorganic particles (total amount of Liquid A and Liquid B).
• the content of the plasticizer is preferably 50 to 700% by mass relative to 100% by mass of the (meth)acrylic polymer in the two-component resin composition. It is more preferably 80 to 600% by mass, even more preferably 100 to 500% by mass, and particularly preferably 150 to 400% by mass.
• the content of the plasticizer is preferably 20 to 500% by mass relative to 100% by mass of the polymerizable monomer. More preferably, it is 50 to 400% by mass, even more preferably, it is 80 to 300% by mass, and particularly preferably, it is 100 to 250% by mass.
• the liquid A and/or the liquid B preferably contain inorganic particles as described below.
• the content of the inorganic particles is not particularly limited, but is preferably 60 to 98% by mass relative to 100% by mass of the two-component resin composition (total amount of Liquid A and Liquid B), which results in a cured product having superior thermal conductivity.
• the content of the inorganic particles is more preferably from 75 to 97% by mass, further preferably from 80 to 96% by mass, and particularly preferably from 85 to 95% by mass.
• the content of the inorganic particles is preferably 400 to 5000% by mass relative to 100% by mass of the total amount of the (meth)acrylic polymer and the polymerizable monomer in the two-component resin composition. It is more preferably 500 to 4500% by mass, even more preferably 600 to 4000% by mass, even more preferably 800 to 3500% by mass, and particularly preferably 1000 to 3000% by mass.
• the above-mentioned solution A and/or solution B may contain other additives as described below.
• the content ratio of the other additives in the two-component resin composition is not particularly limited, but when the inorganic particles are not contained in the A-component and B-component, it is preferably 0 to 30% by mass relative to 100% by mass of the two-component resin composition (total amount of the A-component and B-component), more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass.
• the content of other additives is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass, relative to 100% by mass of the two-component resin composition excluding the inorganic particles (total amount of Liquid A and Liquid B).
• the content of the other additives is preferably 0 to 12% by mass, more preferably 0 to 6% by mass, even more preferably 0 to 2% by mass, and particularly preferably 0 to 1% by mass, based on 100% by mass of the two-component resin composition containing inorganic particles (total amount of Liquid A and Liquid B).
• the above-mentioned solution A contains a polymerizable monomer and a reaction accelerator, the polymerizable monomer includes an aromatic vinyl monomer, and the content of the aromatic vinyl monomer is more than 0 mass% and 60 mass% or less with respect to 100 mass% of the polymerizable monomer.
• the polymerizable monomer is a monomer having at least one polymerizable unsaturated bond.
• the aromatic vinyl monomer is not particularly limited as long as it is a compound having a polymerizable unsaturated bond and an aromatic group, and may be a compound represented by the following formula (1):
• R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• R 4 represents an aryl group or aralkyl group having 6 to 20 carbon atoms which may have a substituent.
• the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, and is 1 or 2, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
• R 1 , R 2 and R 3 are the same or different and each is preferably a hydrogen atom or a methyl group, more preferably R 1 and R 2 are hydrogen atoms and R 3 is a hydrogen atom or a methyl group.
• aryl group examples include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a triphenyl group, and groups having one or more alkyl groups thereon.
• a phenyl group and a group having an alkyl group having 1 to 5 carbon atoms thereon are preferred.
• the aralkyl group examples include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, and a phenyloctyl group.
• the substituents that the aryl group and the aralkyl group may have are not particularly limited, but include hydroxyl groups, carboxyl groups, sulfonic acid groups, amide groups, thiol groups, halogen groups, ether groups, etc.
• the number of carbon atoms in the aryl group and the aralkyl group is preferably 6 to 18, more preferably 6 to 12, even more preferably 6 to 10, and even more preferably 6 to 8.
• the number of carbon atoms in the substituents is also included in the number of carbon atoms.
• R4 is preferably an aryl group, more preferably a phenyl group or an alkylphenylene group.
• the alkyl group in the alkylphenylene group is not particularly limited, and examples thereof include the above-mentioned alkyl groups having 1 to 3 carbon atoms and the below-mentioned alkyl groups having 4 to 14 carbon atoms. More preferred examples of R4 include a phenyl group and a methylphenylene group.
• Preferred examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, vinylnaphthalene, vinylbiphenyl, etc., and more preferably styrene, ⁇ -methylstyrene, and vinyltoluene.
• the polymerizable monomer preferably contains a monomer having a glass transition temperature when homopolymerized of ⁇ 180 to ⁇ 20° C. This enhances the flexibility of the cured product, and when the resin composition is used as a heat dissipation material, it is possible to more sufficiently enhance the conformability of the heat dissipation material to the heat generating body and the heat dissipation body.
• the glass transition temperature is preferably from -160 to -30°C.
• the glass transition temperature means a temperature calculated based on the Fox formula described below.
• the monomer having a glass transition temperature of -180 to -20°C when homopolymerized is not particularly limited, but examples include (meth)acrylates having a hydrocarbon group with 4 to 15 carbon atoms, which may have a substituent, as described below, hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.
• the polymerizable monomer preferably contains a (meth)acrylate having a hydrocarbon group of 4 to 15 carbon atoms, which may have a substituent.
• the (meth)acrylate having a hydrocarbon group of 4 to 15 carbon atoms, which may have a substituent has a bulky structure, and therefore in this case too, the flexibility of the cured product can be increased, so that when used as a heat dissipation material, the conformability of the heat dissipation material to the heat generating body and heat dissipation body can be more sufficiently increased.
• the (meth)acrylate having a hydrocarbon group having 4 to 15 carbon atoms may have a substituent.
• the substituent is not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, an amino group, a phosphoric acid group, an ether group, a thiol group, a thioether group, and a halogen group.
• the number of carbon atoms in the hydrocarbon group may be 4 to 15, but the number of carbon atoms in the hydrocarbon group includes the number of carbon atoms in the substituent.
• the hydrocarbon group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 4 to 8 carbon atoms.
• hydrocarbon group in the (meth)acrylate examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group.
• the above hydrocarbon group preferably has no substituent.
• alkyl groups having 4 to 15 carbon atoms include n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosanyl, i-propyl, sec-butyl, i-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, i-amyl, neopentyl, 1,2-dimethylpropyl, 1,1-di
• aliphatic alkyl groups such as 2-ethylbutyl, 2-ethyl-2-methylpropyl, 1-methylheptyl, 2-ethylhexyl, 1,5-dimethylhexyl, t-octyl, 2,6-dimethyloctyl, 2-butyloctyl, branched nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; and alicyclic alkyl groups such as cyclopropylmethyl, cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, cyclooctyl, cyclohexylpropyl, cyclododecyl, norbornyl (C7), adamantyl (C10), and cyclopentyle
• alkenyl groups having 4 to 15 carbon atoms include 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl groups.
• alkynyl group having 4 to 15 carbon atoms examples include butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, tridecynyl, tetradecynyl, and pentadecynyl groups.
• aryl group having 6 to 15 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.
• Examples of the aralkyl group having 6 to 15 carbon atoms include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
• the hydrocarbon group in the (meth)acrylate is preferably an alkyl group, more preferably an aliphatic alkyl group having a straight or branched chain, even more preferably a dodecyl group, an isodecyl group, a nonyl group, an isononyl group, an octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, or a butyl group, and particularly preferably an octyl group, a 1-methylheptyl group, or a 2-ethylhexyl group.
• (meth)acrylates having a hydrocarbon group having 4 to 15 carbon atoms include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, methylbutyl (meth)acrylate, dimethylpropyl (meth)acrylate, dimethylbutyl (meth)acrylate, ethylbutyl (meth)acrylate, methylpropyl (meth)acrylate,
• the polymerizable monomer preferably includes a monomer having two or more polymerizable unsaturated bonds. Such a monomer acts as a crosslinking agent in the resin composition, and can cure the resin composition more sufficiently.
• a monomer having two or more polymerizable unsaturated bonds include polyfunctional (meth)acrylates having two or more (meth)acrylate groups, polyfunctional allyl esters having two or more allyl groups, and polyfunctional allyl ethers having two or more allyl groups.
• polyfunctional (meth)acrylates include, for example, (poly)ethylene glycol di(meth)acrylates such as tetraethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and bifunctional (meth)acrylates such as trimethylolpropane di(meth)acrylate.
• polyethylene glycol di(meth)acrylates such as tetraethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol
• acrylates trifunctional (meth)acrylates such as (meth)acrylate group-containing cyanurate compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate; pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• (meth)acrylate group-containing cyanurate compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-acryloyloxyethyl) isocyanurate
• polyfunctional allyl esters include, for example, allyl group-containing cyanurate compounds such as triallyl isocyanurate and triallyl cyanurate; and aliphatic polyfunctional allyl esters such as diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, diallyl suberate, diallyl azelate, diallyl sebate, diallyl fumarate, diallyl maleate, triallyl citrate, diallyl tartrate, diallyl itaconate, diallyl citracone, and triallyl trimellitate.
• allyl group-containing cyanurate compounds such as triallyl isocyanurate and triallyl cyanurate
• aliphatic polyfunctional allyl esters such as diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, dial
• the above polyfunctional allyl ethers include, for example, diallyl ether, glycerin diallyl ether, glycerin triallyl ether, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, sorbitol diallyl ether, and 1,3-bis(allyloxy).
• the monomer having two or more polymerizable unsaturated bonds is preferably a polyfunctional (meth)acrylate or a polyfunctional allyl ester, more preferably a (meth)acrylate group-containing cyanurate compound or an allyl group-containing cyanurate compound, and even more preferably tris(2-acryloyloxyethyl) isocyanurate or triallyl isocyanurate.
• the polymerizable monomer may include other polymerizable monomers other than aromatic vinyl monomers, monomers having a glass transition temperature of ⁇ 180 to ⁇ 20° C. when homopolymerized, (meth)acrylates having a hydrocarbon group having 4 to 15 carbon atoms which may have a substituent, and monomers having two or more polymerizable unsaturated bonds.
• Examples of other polymerizable monomers include, but are not limited to, alkyl (meth)acrylates having 1 to 3 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; vinyl group-containing monomers, such as N-vinyl-2-pyrrolidone; and reactive light stabilizers, such as 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
• the content of the monomer having a glass transition temperature of -180 to -20°C when homopolymerized is not particularly limited, but is preferably 30 to 99.5% by mass relative to 100% by mass of the polymerizable monomer. More preferably, it is 35 to 99% by mass, even more preferably 40 to 98% by mass, and particularly preferably 50 to 97% by mass.
• the content of the (meth)acrylate having a hydrocarbon group having 4 to 15 carbon atoms, which may have a substituent, is not particularly limited, but is preferably 30 to 99.5% by mass relative to 100% by mass of the polymerizable monomer. It is more preferably 35 to 99% by mass, even more preferably 40 to 98% by mass, and particularly preferably 50 to 97% by mass.
• the content of the monomer having two or more polymerizable unsaturated bonds is not particularly limited, but is preferably 0.1 to 10% by mass relative to 100% by mass of the polymerizable monomer. More preferably, it is 0.2 to 8% by mass, even more preferably, it is 0.5 to 6% by mass, and particularly preferably, it is 1 to 4% by mass.
• the content of the other polymerizable monomers is not particularly limited, but is preferably 0 to 10% by mass relative to 100% by mass of the polymerizable monomers. More preferably, it is 0 to 5% by mass, even more preferably 0 to 1% by mass, particularly preferably 0 to 0.1% by mass, and most preferably 0% by mass.
• the reaction accelerator preferably contains a metal compound, which can more sufficiently increase the monomer conversion rate during curing.
• the metal compound may be any compound containing a transition metal element such as cobalt, iron, manganese, copper, zinc, titanium, chromium, vanadium, zirconium, etc., but is preferably a salt (complex) of an organic compound having 4 to 20 carbon atoms with the transition metal element.
• the metal compound include metal soaps such as cobalt naphthenate, iron naphthenate, manganese naphthenate, copper naphthenate, zinc naphthenate, cobalt octylate, iron octylate, cobalt neodecanoate, copper neodecanoate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, and vanadyl acetylacetonate.
• metal soaps such as cobalt naphthenate, iron naphthenate, manganese naphthenate, copper naphthenate, zinc naphthenate, cobalt octylate, iron octylate, cobalt neodecanoate, copper neodecano
• the metal element in the metal compound is preferably cobalt, iron or manganese, and more preferably cobalt.
• the metal compound is preferably cobalt naphthenate, cobalt octylate, or cobalt acetylacetonate, and more preferably cobalt naphthenate or cobalt octylate.
• the reaction accelerator may contain a compound other than the metal compound.
• the reaction accelerator other than the above metal compound is not particularly limited, and examples thereof include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-cyanoethyl-2-methylimidazo compounds having an imidazole skeleton such as aniline, N,N-dimethylaniline, N,N-diethylaniline, m-toluidine, p-toluidine, N-ethyl-m-toluidine, N,N-dimethyl compounds having an aniline skeleton, such as N,N-p-toluidine, N,N-bis
• compounds having an alkanolamine skeleton and thiourea compounds are preferred. More preferred compounds having an alkanolamine skeleton are compounds having an ethanolamine skeleton, and even more preferred are p-tolyldiethanolamine and N-phenyldiethanolamine.
• the thiourea compound is preferably a dialkylthiourea, and more preferably dibutylthiourea.
• the liquid A preferably contains a plasticizer, which makes the resin composition excellent in processability even in the absence of a solvent.
• Trimellitic acid triester plasticizers such as tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, and triisononyl trimellitate; phthalic acid ester plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, ditridecyl phthalate, and diundecyl phthalate; di-n-butyl adipate, diisobutyl adipate, and dibutoxyethyl Adipate-based plasticizers such as adipate, di-n-oc
• azelaic acid ester-based plasticizers such as dihexyl azelate and dioctyl azelate; citrate ester-based plasticizers such as triethyl citrate, acetyl triethyl citrate, and tri-n-butyl citrate; glycolic acid ester-based plasticizers such as methyl phthalyl ethyl glycolate and ethyl phthalyl ethyl glycolate; trimellitic acid triester-based plasticizers such as trioctyl trimellitate, tri-n-octyl-n-decyl trimellitate, and trialkyl trimellitate (alkyl group carbon number: 4 to 11); methyl acetyl lysine
• suitable plasticizers include ricinoleic acid ester plasticizers such as di-n-butyl maleate, butyl acetyl ricinoleate, and glycerin monoricinoleate; male
• plasticizers may be used alone or in combination of two or more kinds.
• trimellitic acid triester plasticizers are preferred from the viewpoint of preventing the vaporization of the plasticizer and improving the thermal stability of the plasticizer over a long period of time.
• the liquid A may contain a (meth)acrylic polymer.
• the component B may contain a (meth)acrylic polymer, or the components A and/or B may contain a (meth)acrylic polymer.
• Such an embodiment is one of the preferred embodiments of the present invention.
• the (meth)acrylic polymer has a structural unit derived from a (meth)acrylic monomer.
• the structural unit derived from a (meth)acrylic monomer is a unit having a structure in which the carbon-carbon double bond of the (meth)acrylic monomer is replaced with a carbon-carbon single bond.
• the structural unit derived from a (meth)acrylic monomer can be introduced into a (meth)acrylic polymer by polymerizing the (meth)acrylic monomer.
• Examples of (meth)acrylic monomers include alkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, etc., but the present invention is not limited to these examples. These (meth)acrylic monomers may be used alone or in combination of two or more kinds.
• alkyl (meth)acrylate examples include alkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms. Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and the above-mentioned alkyl (meth)acrylates in which the alkyl group has 4 to 15 carbon atoms. These alkyl (meth)acrylates may be used alone or in combination of two or more.
• alkyl (meth)acrylates from the viewpoint of increasing the flexibility of the cured product and increasing the conformability to a heat generating body and a heat dissipating body when the cured product is used as a heat dissipating material, alkyl (meth)acrylates having an alkyl group of 1 to 8 carbon atoms are preferred, and n-butyl (meth)acrylate, n-octyl (meth)acrylate, 1-methylheptyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are more preferred.
• the content ratio of the structural units derived from alkyl (meth)acrylate in the (meth)acrylic polymer is not particularly limited, but from the viewpoint of improving the conformity of the heat dissipating material to the heat generating body and the heat dissipating body, it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to 100% by mass of all structural units, with the upper limit being 100% by mass.
• the content ratio of alkyl (meth)acrylate in the (meth)acrylic monomer is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, even more preferably 70 to 98% by mass, and particularly preferably 80 to 97% by mass.
• hydroxyl group-containing (meth)acrylates examples include hydroxyl group-containing (meth)acrylates having an ester moiety with 1 to 18 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate, but the present invention is not limited to these examples.
• These hydroxyl group-containing (meth)acrylates may be used alone or in combination of two or more kinds.
• hydroxyl group-containing (meth)acrylates from the viewpoint of reactivity, 2-hydroxyethyl (meth)acrylate and glycerin mono(meth)acrylate are preferred, 2-hydroxyethyl (meth)acrylate is more preferred, and 2-hydroxyethyl acrylate is even more preferred. Furthermore, from the viewpoint of improving the dispersion stability of inorganic particles in Liquid A when inorganic particles described below are contained in Liquid A, 2-hydroxyethyl (meth)acrylate and glycerin mono(meth)acrylate are preferred, 2-hydroxyethyl (meth)acrylate is more preferred, and 2-hydroxyethyl acrylate is even more preferred.
• the content ratio of the structural unit derived from the hydroxyl group-containing (meth)acrylate in the (meth)acrylic polymer is preferably 0% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of all structural units, from the viewpoint of improving the dispersion stability of the resin composition and reducing the viscosity of the resin composition, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on the viewpoint of reducing the viscosity of the (meth)acrylic polymer and improving the compatibility between the (meth)acrylic monomer and the radical polymerizable monomer.
• the content ratio of the hydroxyl group-containing (meth)acrylate in the (meth)acrylic monomer is preferably 0 to 30% by mass, more preferably 0.3 to 30% by mass, even more preferably 0.5 to 20% by mass, and even more preferably 1 to 20% by mass, based on 100% by mass of all structural units.
• the (meth)acrylic polymer may contain structural units derived from monomers other than the above-mentioned monomers, as long as the object of the present invention is not impaired.
• the other monomers include cycloalkyl (meth)acrylates such as cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; carbon-carbon double bond-containing monomers having a carboxyl group such as (meth)acrylic acid; carbon-carbon double bond-containing monomers having a silane group; carbon-carbon double bond-containing monomers having a nitrogen atom; carbon-carbon double bond-containing monomers having an oxo group; carbon-carbon double bond-containing monomers having a fluorine atom; carbon-carbon double bond-containing monomers having an epoxy group; carbon-carbon double bond-containing monomers having an aralkyl group
• the content of structural units derived from other monomers in the (meth)acrylic polymer is not particularly limited, but is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, even more preferably 0 to 0.1% by mass, and most preferably 0% by mass, relative to 100% by mass of all structural units.
• the (meth)acrylic polymer can be prepared by polymerizing a monomer component containing a (meth)acrylic monomer by a polymerization method such as bulk polymerization, solution polymerization, or emulsion polymerization.
• a polymerization method such as bulk polymerization, solution polymerization, or emulsion polymerization.
• bulk polymerization is preferred from the viewpoint of preventing the inclusion of the solvent and dispersion medium in the (meth)acrylic polymer.
• the glass transition temperature of the (meth)acrylic polymer is preferably -20°C or lower, more preferably -30°C or lower, from the viewpoint of increasing the flexibility of the cured product and increasing the conformability to heat generating bodies and heat dissipating bodies when the cured product is used as a heat dissipating material.
• the lower limit of the glass transition temperature of the (meth)acrylic polymer is not particularly limited, but is preferably -200°C or higher, more preferably -180°C or higher.
• the term "temperature” refers to the temperature calculated based on the Fox equation
• the glass transition temperature of a polymer means the glass transition temperature calculated based on the formula (3). For monomers whose glass transition temperatures are unknown, the glass transition temperature is calculated using only monomers whose glass transition temperatures are known.
• the composition of the radical polymerizable monomers used as raw materials for the polymer can be determined in consideration of the glass transition temperature of the polymer.
• the glass transition temperatures of the homopolymers are, for example, 105°C for a homopolymer of methyl methacrylate, 8°C for a homopolymer of methyl acrylate, -20°C for a homopolymer of ethyl acrylate, -56°C for a homopolymer of n-butyl acrylate, 20°C for a homopolymer of n-butyl methacrylate, -80°C for a homopolymer of n-octyl acrylate, -58°C for a homopolymer of isooctyl acrylate, -70°C for a homopolymer of 2-ethylhexyl acrylate, and -80°C for a homopolymer of cyclohexyl acrylate.
• the temperature is 16°C; for homopolymers of cyclohexyl methacrylate, the temperature is 83°C; for homopolymers of 2-hydroxyethyl acrylate, the temperature is -15°C; for homopolymers of 2-hydroxyethyl methacrylate, the temperature is 55°C; for homopolymers of 4-hydroxybutyl acrylate, the temperature is -40°C; for homopolymers of acrylic acid, the temperature is 106°C; for homopolymers of methacrylic acid, the temperature is 105°C; for homopolymers of styrene, the temperature is 80°C; and for homopolymers of N-vinylpyrrolidone, the temperature is 170°C.
• the glass transition temperature of a (meth)acrylic polymer means a temperature determined based on the above-mentioned method for measuring the glass transition temperature of a polymer.
• the glass transition temperature of the (meth)acrylic polymer can be easily adjusted by appropriately adjusting the type and amount of the (meth)acrylic monomer that is the raw material of the (meth)acrylic polymer.
• the weight average molecular weight of the (meth)acrylic polymer is not particularly limited, but is preferably from 10,000 to 1,500,000, more preferably from 20,000 to 1,000,000, even more preferably from 30,000 to 500,000, and still more preferably from 50,000 to 300,000. In one embodiment, the weight average molecular weight of the (meth)acrylic polymer may be 100,000 or more, or 150,000 or more.
• the weight average molecular weight of the (meth)acrylic polymer is a value calculated using a gel permeation chromatography (GPC) measuring apparatus (product number: HLC-8220GPC, manufactured by Tosoh Corporation) and a separation column (product number: TSKgel Super HZM-M, manufactured by Tosoh Corporation) converted into a standard polystyrene (manufactured by Tosoh Corporation).
• GPC gel permeation chromatography
• the two-component resin composition of the present invention preferably contains inorganic particles, and at least one of the above-mentioned Liquid A and the below-described Liquid B preferably contains inorganic particles, which can improve the thermal conductivity of the cured product.
• the inorganic particles are not particularly limited, and examples thereof include alkali metal carbonate particles such as sodium carbonate particles, sodium bicarbonate particles, potassium carbonate particles, and potassium bicarbonate particles; alkaline earth metal carbonate particles such as magnesium carbonate particles, calcium carbonate particles, and barium carbonate particles; carbonate particles such as ammonium carbonate particles and ammonium bicarbonate particles, zinc oxide particles, aluminum oxide particles, magnesium oxide particles, beryllium oxide particles, calcium oxide particles, zirconium oxide particles, aluminum oxide (alumina) particles, titanium dioxide particles, silica particles, magnesium hydroxide particles, aluminum hydroxide particles, calcium silicate particles, aluminum silicate particles, silicon carbide particles, silicon nitride particles, boron nitride particles, calcium sulfate particles, barium sulfate particles, magnesium carbonate particles, glass particles, kaolin, talc, mica powder, metal particles, and carbon black particles. These inorganic particles may be used alone or in combination of two or more. Among these, aluminum oxide (a
• the average particle size of the inorganic particles is preferably 0.3 ⁇ m or more from the viewpoint of preventing aggregation of the inorganic particles. More preferably, it is 0.5 ⁇ m or more, and even more preferably, it is 1 ⁇ m or more. Furthermore, from the viewpoint of improving the dispersion stability of the inorganic particles, the average particle size is preferably 100 ⁇ m or less. More preferably, it is 80 ⁇ m or less, and even more preferably, it is 50 ⁇ m or less. Therefore, the average particle size of the inorganic particles is preferably 0.3 to 100 ⁇ m, more preferably 0.5 to 80 ⁇ m, and even more preferably 1 to 50 ⁇ m.
• the average particle size of the inorganic particles means the volume average particle size measured using a particle size distribution measuring device by the laser diffraction scattering method [manufactured by Beckman Coulter, Inc., product number: LS13320].
• the solution B is characterized by containing an initiator.
• the initiator is not particularly limited as long as it can initiate the polymerization reaction of the polymerizable monomer, and examples thereof include ketone peroxide-based polymerization initiators, hydroperoxide-based polymerization initiators, diacyl peroxide-based polymerization initiators, peroxyester-based polymerization initiators, peroxyketal-based polymerization initiators, dialkyl peroxide-based polymerization initiators, peroxydicarbonate-based polymerization initiators, etc. These polymerization initiators may be used alone or in combination of two or more kinds. As the above-mentioned initiator, preferred are hydroperoxide-based polymerization initiators, diacyl peroxide-based polymerization initiators, and peroxy ester-based polymerization initiators.
• ketone peroxide polymerization initiator examples include methyl ethyl ketone peroxide, cyclohexane peroxide, methylcyclohexane peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
• hydroperoxide-based polymerization initiator examples include p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, and tert-butyl hydroperoxide.
• cumene hydroperoxide and tert-butyl hydroperoxide are preferred.
• diacyl peroxide polymerization initiator examples include diisobutyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, disuccinic acid peroxide, m-toluoyl peroxide, m-benzoyl peroxide, benzoyl peroxide, etc.
• m-benzoyl peroxide and benzoyl peroxide are preferred.
• peroxy ester polymerization initiator examples include t-butyl peroxybenzoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, and t-butylperoxy-2-ethylhexyl monocarbonate.
• t-butylperoxybenzoate is preferred.
• the peroxyketal polymerization initiator include 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, n-butyl-4,4-di(t-butylperoxy)valerate, and 2,2-di(tert-butylperoxy)butane.
• dialkyl peroxide polymerization initiator examples include dicumyl peroxide, ⁇ , ⁇ '-di(tert-butylperoxy)diisopropylbenzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane-3.
• peroxydicarbonate polymerization initiator examples include diperoxydicarbonate polymerization initiators such as diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate.
• reaction Accelerator Auxiliary Agent The above-mentioned solution B preferably contains a reaction promotion aid.
• the reaction promotion aid preferably contains a diketone compound.
• the diketone compound may be any compound having two carbonyl groups, and may be represented by the following formula (4):
• R 5 , R 6 and R 7 are the same or different and each represents an organic group.
• R 5 and R 6 and/or R 6 and R 7 may be bonded to each other to form a ring structure).
• the organic group include a hydrocarbon which may have a heteroatom, an amino group, a carboxyl group, a thiol group, a cyano group, and a halogen group.
• the number of carbon atoms in the hydrocarbon which may have a heteroatom is not particularly limited, but is preferably 1 to 20. It is more preferably 1 to 15, even more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 1 to 6.
• hydrocarbons may have heteroatoms, and may have substituents having heteroatoms, such as amino groups, carboxyl groups, thiol groups, cyano groups, halogen groups, hydroxyl groups, ether groups, ester groups, and thioether groups.
• the above-mentioned hydrocarbon group includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a group obtained by abstracting a hydrogen atom from a heterocyclic compound.
• the alkyl group may be any of the above-mentioned alkyl groups having 4 to 15 carbon atoms, aliphatic alkyl groups such as methyl, ethyl, propyl, isopropyl, hexadecyl, heptadecyl, stearyl, and icosyl, and alicyclic alkyl groups such as cyclopropyl.
• the above-mentioned alkenyl group includes the above-mentioned alkenyl groups having 4 to 15 carbon atoms, vinyl groups, allyl groups, hexadecenyl groups, heptadecenyl groups, octadecenyl groups, icosinyl groups, etc.
• the above alkynyl group and aryl group include the above alkynyl group having 4 to 15 carbon atoms, the above aryl group having 6 to 15 carbon atoms, and the above aralkyl group having 6 to 15 carbon atoms.
• the heterocyclic compounds include imidazole, imidazolidine, pyrazole, benzimidazole, pyridine, pyrimidine, pyrazine, pyridazine, pyrrole, pyrroline, thiophene, furan, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, carbazole, thiazole, benzothiazole, oxazole, benzoxazole, quinoline, isoquinoline, quinoxaline, benzothiadiazole, phenanthridine, oxadiazole, and thiadiazole.
• R5 is preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a phenyl group, more preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a phenyl group, and further preferably a methyl group.
• R 6 and R 7 are preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a phenyl group, or a form in which R 6 and R 7 are bonded together to form a ring structure having 3 to 8 carbon atoms, more preferably a form in which R 6 and R 7 are bonded together to form a lactone structure having 3 to 8 carbon atoms.
• the lactone structure preferably has 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 to 5 carbon atoms.
• the diketone compound include ⁇ -acetyl- ⁇ -butyrolactone, ethyl cyclopentanone-2-carboxylate, methyl cyclopentanone-2-carboxylate, acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-butyl acetoacetate, isopropyl acetoacetate, allyl ether acetoacetate, diethyl 1,1-cyclopropanedicarboxylate, dimethyl malonate, diethyl malonate, dipropyl malonate, diisopropyl malonate, tert-butylethyl malonate, dimethyl methylmalonate, diethyl ethylmalonate, 1,3-diphenyl-1,3-propanedione, acetoacetamide, N-methylamyl malonate, diethyl ethylmalonate, methyl
• acetoacetamide examples include acetoacetamide, N,N-dimethylacetoacetamide, N,N-diethylacetoacetamide, N,N-diisopropylacetoacetamide, N,N-dibutylacetoacetamide, N,N-dihydroxyethylacetoacetamide, N-methylacetoacetanilide, 1-acetoacetylpyrrolidine, 1-acetoacetylindole, 1-acetoacetylimidazole, 1-acetoacetylpyrrole, 1-acetoacetylimidazoline, 1-acetoacetylpyrroline, 1-acetoacetylimidazolidine, 1-acetoacetylpiperidine, 1-acetoacetylpiperazine, and N-pyrrolidininoacetoacetamide.
• ⁇ -acetyl- ⁇ -butyrolactone dimethyl malonate, diethyl malonate, ethyl cyclopentanone-2-carboxylate, and 1,3-diphenyl-1,3-propanedione, and more preferred is ⁇ -acetyl- ⁇ -butyrolactone.
• the liquid B preferably contains a (meth)acrylic polymer, which allows the inorganic particles to be dispersed more thoroughly.
• the embodiment in which the above-mentioned solution A and solution B each contain a (meth)acrylic polymer is one of the preferred embodiments of the present invention.
• the (meth)acrylic polymer contained therein may be the same or different.
• one of the preferred embodiments of the present invention is one in which one of the liquids A and B contains a (meth)acrylic polymer having a weight average molecular weight of 10,000 to 150,000, and the other contains a (meth)acrylic polymer having a weight average molecular weight of 150,000 to 1,500,000.
• the liquid B may contain inorganic particles. Specific examples and preferred examples of the inorganic particles are the same as those described in relation to Solution A.
• the embodiment in which the above-mentioned solutions A and B contain inorganic particles is one of the preferred embodiments of the present invention.
• the inorganic particles contained in each liquid may be the same or different.
• liquid A and/or liquid B may each contain other additives within the scope of the present invention.
• other additives include colorants such as pigments, leveling agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, metal deactivators, wetting agents, defoamers, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosive agents, pigment dispersants, flow regulators, peroxide decomposers, mold decolorizing agents, fluorescent brighteners, organic flame retardants, inorganic flame retardants, drip prevention agents, melt flow modifiers, antistatic agents, algae inhibitors, fungicides, flame retardants, slip agents, metal chelating agents, antiblocking agents, heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, antiaging agents, preservatives, antistatic agents, silane coupling agents, antioxidant
• the method for preparing the above-mentioned solutions A and B is not particularly limited, and each solution can be prepared by mixing the essential components and optional components using a batch mixer, a tumbler, a Henschel mixer, a Banbury mixer, a roll, a kneader, a single-screw extruder, a twin-screw extruder, or the like.
• the temperature at which the above components are mixed is not particularly limited, and may be room temperature, a temperature higher than room temperature, or a temperature lower than room temperature.
• the atmosphere in which the above components are mixed is not particularly limited and may be air. However, from the viewpoint of avoiding the influence of oxygen gas contained in the air, an inert gas such as nitrogen gas or argon gas may be used.
• the two-component resin composition of the present invention comprises the components A and B obtained as described above.
• the ratio of the liquid A to the liquid B is preferably adjusted so that the components contained in the liquid A and the liquid B are in the preferred ratio described above.
• the amount of Liquid A excluding the inorganic particles per 100 parts by mass of Liquid B is preferably about 3 to 300 parts by mass, taking into consideration the convenience when mixing Liquid A and Liquid B.
• the amount of Liquid A excluding the inorganic particles per 100 parts by mass of Liquid B is preferably about 3 to 300 parts by mass, taking into consideration the convenience when mixing Liquid A and Liquid B.
• liquid A and liquid B when liquid A and liquid B are mixed, they react with each other quickly even at room temperature, so that it is not necessary to produce a cured product such as a heat dissipating material by heating as in the conventional method. Therefore, it is possible to efficiently produce a cured product such as a heat dissipating material on a production line in a factory, for example.
• a stirring device When mixing the A liquid and the B liquid, a stirring device can be used.
• the stirring device include a batch mixer, a tumbler, a Henschel mixer, a Banbury mixer, a roll, a kneader, a single screw extruder, and a twin screw extruder, but the present invention is not limited to only these examples.
• the temperature when mixing the A liquid and the B liquid is not particularly limited, but from the viewpoint of efficiently producing a cured product such as a heat dissipation material without using a device such as a heating device or a cooling device, it is preferably room temperature.
• the room temperature cannot be determined in general because it varies depending on the region, but it is usually 0 to 40°C, preferably 0 to 35°C, and more preferably 1 to 30°C.
• the temperature when mixing the A liquid and the B liquid may be a temperature above room temperature or a temperature below room temperature as necessary, but from the viewpoint of efficiently producing a cured product such as a heat dissipation material, it is preferably a temperature of about 0 to 50°C.
• the atmosphere when mixing the A liquid and the B liquid is not particularly limited and may be air, but from the viewpoint of avoiding the influence of oxygen gas contained in the air, it may be an inert gas such as nitrogen gas or argon gas.
• the end point of hardening of the mixed liquid can be the tack-free time of the surface of the hardened product obtained from the mixed liquid.
• the tack-free time means the time from the time when liquid A and liquid B are mixed to the time when the components of the hardened product no longer adhere to the finger of a person who has removed oils and fats with ethanol or the like when touching the surface of the hardened product formed by hardening the mixed liquid of liquid A and liquid B with the finger of the person.
• the two-component resin composition of the present invention can be suitably used as a resin for heat dissipation materials, an adhesive, a pressure sensitive adhesive, and the like.
• the present invention also relates to use of the two-component resin composition of the present invention as a resin for heat dissipation materials, an adhesive, or a pressure sensitive adhesive.
• the present invention also relates to a heat dissipating material obtained by curing the above two-component resin composition.
• the present invention also relates to a method for producing a heat dissipating material, which comprises a step of curing the two-component resin composition of the present invention.
• the shape of the heat dissipating material obtained by using the two-component resin composition of the present invention is not particularly limited.
• a heat dissipating material having a sheet or tape shape can be produced by, for example, mixing liquid A and liquid B, forming a coating on a substrate with the resulting mixed liquid using, for example, a brush, a bar coater, an applicator, an air spray, an airless spray, a roll coater, a flow coater, or the like, and curing the formed coating, or by mixing liquid A and liquid B, extruding the resulting mixed liquid from an extrusion molding machine through a T-die to form a sheet or film, and curing the resulting mixture.
• a heat dissipating material having a cylindrical shape can be produced by, for example, mixing liquid A and liquid B, extruding the resulting mixed liquid from an extrusion molding machine through a spider to form a cylindrical heat dissipating material, and curing the resulting mixture.
• a heat dissipating material having a desired molded shape can be produced, for example, by mixing liquid A and liquid B, and molding the resulting mixture into the desired shape using an injection molding machine or the like.
• the thermal conductivity of the heat dissipation material can be adjusted, for example, by adjusting the amount of inorganic particles used as the thermally conductive material.
• the thermal conductivity of the heat dissipation material is not particularly limited, but from the viewpoint of improving the heat dissipation performance of the heat dissipation material, it is preferably 0.5 W/m ⁇ K or more, and more preferably 1 W/m ⁇ K or more.
• the thermal conductivity of the heat dissipation material is the value measured at a temperature of 25°C using a rapid thermal conductivity meter (product number: QTM-500) manufactured by Kyoto Electronics Manufacturing Co., Ltd.
• Heating conditions 40°C, hold for 5 min ⁇ Heat from 40°C to 230°C at a rate of 15°C/min ⁇ Hold at 230°C for 10 min
• ⁇ The monofunctional monomer conversion rate is 97% or more.
• ⁇ The monofunctional monomer conversion rate is 90% or more and less than 97%.
• Liquid A was prepared by mixing 1.2 g of cobalt phthenate (manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt) and 1.5 g of tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., product name: M-313) as a crosslinking agent at room temperature (approximately 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to Liquid A and mixed until a uniform composition was obtained, and the resulting mixture was used as Liquid A.
• cobalt phthenate manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt
• tris(2-acryloyloxyethyl) isocyanurate manufactured by Toagosei Co., Ltd., product name: M-313
• Liquid B was prepared by mixing 5 g of a polymerization initiator (a mixture of tert-butyl peroxybenzoate and cumene hydroperoxide) [manufactured by Kayaku Nouryon Co., Ltd., product name: 328E] as a polymerization initiator at room temperature (about 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to liquid B and mixed until a uniform composition was obtained, and the resulting mixture was used as liquid B.
• a two-part curable composition (two-part resin composition) was prepared using the above-obtained liquids A and B, and its physical properties were examined as described above. The results are shown in Table 1.
• Liquid A was prepared by mixing 10 g of ethyl acetate, 1.2 g of cobalt naphthenate [manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt], and 1.5 g of tris(2-acryloyloxyethyl) isocyanurate [manufactured by Toagosei Co., Ltd., product name: M-313] as a crosslinking agent at room temperature (approximately 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to Liquid A and mixed until a uniform composition was obtained, and the resulting mixture was used as Liquid A.
• Example 3 [Preparation of Solution A]
• Liquid A was prepared by mixing 5 g of isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt), 1.2 g of cobalt naphthenate (manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt), and 1.5 g of tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., product name: M-313) as a crosslinking agent at room temperature (approximately 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to Liquid A and mixed until a uniform composition was obtained, and the resulting mixture was used as Liquid A.
• isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt
• cobalt naphthenate manufactured by Tokyo Chemical Industry Co
• Liquid A was prepared by mixing 1.2 g of cobalt phthenate (manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt) and 1.5 g of tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., product name: M-313) as a crosslinking agent at room temperature (approximately 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to Liquid A and mixed until a uniform composition was obtained, and the resulting mixture was used as Liquid A.
• cobalt phthenate manufactured by Tokyo Chemical Industry Co., Ltd., containing approximately 8% cobalt
• tris(2-acryloyloxyethyl) isocyanurate manufactured by Toagosei Co., Ltd., product name: M-313
• Liquid B was prepared by mixing 5 g of a polymerization initiator (a mixture of tert-butyl peroxybenzoate and cumene hydroperoxide) [manufactured by Kayaku Nouryon Co., Ltd., product name: 328E] as a polymerization initiator at room temperature (about 25° C.) in the air until a uniform composition was obtained, and 733 g of alumina powder (average particle size: 10 ⁇ m) was added to liquid B and mixed until a uniform composition was obtained, and the resulting mixture was used as liquid B.
• a two-part curable composition was prepared using the above-obtained liquids A and B, and the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

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