Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/602—Dicarboxylic acid esters having at least two carbon-to-carbon double bonds
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present invention relates to a composition containing a compound having a polyoxyalkylene chain.
• a heat conductive material (sometimes called a heat radiating material) called a thermal interface material (TIM) is used in order to dissipate heat efficiently.
• the TIM contains, for example, polymers and thermally conductive fillers.
• a suitable polymer is selected according to the application (application target) of TIM.
• a composition containing a polymer may be required to have a low viscosity and excellent handleability, and a cured product of the composition may be required to have a low elasticity.
• Patent Document 1 discloses a curable silicone composition that has good handling workability and forms a cured product having a low elastic modulus.
• an object of the present invention is to improve the breakability of the cured product of the composition while improving the handleability of the composition.
• the present invention provides the following [1] to [7] in some aspects.
• [3] The composition according to [1], wherein the polyoxyalkylene chain contains an oxypropylene group.
• (meth) acryloyl means “acryloyl” and the corresponding “methacryloyl”, and the same applies to similar expressions such as “(meth) acrylate” and “(meth) acrylic”. ..
• the weight average molecular weight (Mw) in the present specification means a value determined by using gel permeation chromatography (GPC) under the following conditions and using polystyrene as a standard substance.
• GPC gel permeation chromatography
• -Analytical column TSKgel SuperMultipore HZ-H (3 connected) (Product name, manufactured by Tosoh Corporation) -Guard column: TSKguardvolume SuperMP (HZ) -H (product name, manufactured by Tosoh Corporation) -Eluent: THF ⁇ Measurement temperature: 25 ° C
• One embodiment of the present invention is a composition containing 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, and 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 number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.
• the composition of the present embodiment has a structure represented by the formula (1) and contains a compound having 100 or more oxyalkylene groups in the polyoxyalkylene chain, so that the composition has a low viscosity and is easy to handle. It is possible to form a cured product having an excellent elongation at break while being excellent in Further, in one embodiment, the cured product of this composition may have low elasticity and high strength. From these viewpoints, the number of oxyalkylene groups in the polyoxyalkylene chain is 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 polyoxyalkylene chain contains an oxyethylene group (in other words, a structural unit represented by the following formula (2)).
• R 13 may be a divalent group having a polyoxyethylene chain
• the compound represented by the formula (1) is preferably a compound represented by the following formula (1-2) (polyethylene glycol di). (Meta) acrylate).
• R 11 and R 12 have the same meanings as R 11 and R 12 in the formula (1)
• m is 100 or more integer.
• m can take the same lower limit value and upper limit value as the number of oxyalkylene groups described above.
• the polyoxyalkylene chain comprises an oxypropylene group (in other words, a structural unit represented by the following formula (3)). This makes the handling of the composition even easier.
• R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by the formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di). (Meta) acrylate).
• (1-3) polypropylene glycol di).
• R 11 and R 12 have the same meanings as R 11 and R 12 in the formula (1)
• n is 100 or more integer.
• m can take the same lower limit value and upper limit value as the number of oxyalkylene groups described above.
• the polyoxyalkylene chain is preferably an oxyethylene group and an oxypropylene from the viewpoint of further facilitating the handleability of the composition and the low elasticity, high elongation and high strength of the cured product. It is a copolymer chain containing a group.
• the copolymer chain may be any of an alternating copolymer chain, a block copolymer chain, and a random copolymer chain.
• the copolymer chain is preferably a random copolymer chain from the viewpoint of facilitating the handling of the composition.
• the polyoxyalkylene chain has an oxyalkylene group having 4 to 5 carbon atoms, such as an oxytetramethylene group, an oxybutylene group, and an oxypentylene group, in addition to the oxyethylene group and the oxypropylene group. It may have as a unit.
• R 13 may be a divalent group having another organic group in addition to the polyoxyalkylene chain described above.
• Other organic groups may be polyoxyalkylene chain non-chain groups, for example, methylene chain (-CH 2 - chain to the structural units), containing polyester chain (-COO- into the structural unit Chain), polyurethane chain (chain containing —OCON— in the structural unit) and the like.
• the compound represented by the formula (1) may be a compound represented by the following formula (1-4).
• R 11 and R 12 have the same meanings respectively as R 11 and R 12 in the formula (1)
• R 14 and R 15 are each independently an alkylene group having 2 to 5 carbon atoms
• K1 and k3 are each independently an integer of 100 or more
• k2 is an integer of 2 or more.
• K1 and k3 can independently take the same lower limit value and upper limit value as the number of oxyalkylene groups described above.
• k2 may be, for example, an integer of 16 or less.
• a plurality of R 14 and R 15 may be the same as each other or may be different from each other.
• the plurality of R 14 and R 15 preferably contain 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 preferably copolymerized containing an oxyethylene group and an oxypropylene group, respectively. It is a chain.
• the weight average molecular weight of the compound represented by the formula (1) is preferably 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, 10000 or more, 11000 from the viewpoint that the cured product has lower elasticity and excellent elongation. 12000 or more, 13000 or more, 14000 or more, or 15000 or more.
• the weight average molecular weight of the compound represented by the formula (1) is preferably 100,000 or less, 80,000 or less, 60,000 or less, 40,000 or less, or 30,000 or less from the viewpoint of making it easier to adjust the viscosity of the composition.
• the compound represented by the formula (1) may be liquid at 25 ° C.
• the viscosity of the compound represented by the formula (1) at 25 ° C. is preferably 500 Pa ⁇ s or less, more preferably 350 Pa ⁇ s or less, still more preferably 300 Pa ⁇ s, from the viewpoint of further improving the handleability of the composition. -S or less, particularly preferably 200 Pa or less.
• the viscosity of the compound represented by the formula (1) at 25 ° C. may be 0.1 Pa ⁇ s or more, 0.2 Pa ⁇ s or more, or 0.3 Pa ⁇ s or more.
• the compound represented by the formula (1) may be in a solid state at 25 ° C.
• the compound represented by the formula (1) is preferably liquid at 50 ° C. from the viewpoint of further improving the handleability of the composition.
• the viscosity of the compound represented by the formula (1) at 50 ° C. is preferably 100 Pa ⁇ s or less, more preferably 50 Pa ⁇ s or less, still more preferably, from the viewpoint of further improving the handleability of the composition. Is 30 Pa ⁇ s or less, particularly preferably 20 Pa ⁇ s or less.
• the viscosity of the compound represented by the 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 Z 8803, and specifically, a value measured by an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.).
• the calibration of the viscometer can be performed based on JIS Z 8809-JS14000.
• the viscosity of the compound represented by the formula (1) can be adjusted by adjusting the weight average molecular weight of the compound.
• the content of the compound represented by the formula (1) is, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, and 40% by mass based on the total amount of the composition. % Or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass. % Or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.
• the composition may contain only the compound represented by the formula (1) as the polymerizable compound.
• the composition may further contain a polymerizable compound (details will be described later) other than the compound represented by the formula (1).
• the content of the compound represented by the formula (1) is, for example, the total of the compound represented by the formula (1) and other polymerizable compounds (hereinafter, referred to as "the total content of the polymerizable component").
• It may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts. It may be less than or equal to a mass part.
• the composition may further contain other polymerizable compounds that can be copolymerized with the compound represented by the above formula (1) for the purpose of adjusting the physical properties of the composition.
• the other polymerizable compound may be, for example, a compound having one (meth) acryloyl group.
• 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, and the like. 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 adjusted by containing the alkyl (meth) acrylate in the composition.
• 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 to the composition and the cured product thereof is further improved. it can.
• the alkyl group (alkyl group portion other than the (meth) acryloyl group) in the alkyl (meth) acrylate may be linear, branched or alicyclic.
• the number of carbon atoms of the alkyl group may be, for example, 1 to 30.
• the alkyl group may have 1 to 11, 1 to 8, 1 to 6, or 1 to 4, and may have 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 carbon atoms. It may be up to 14.
• alkyl (meth) acrylate having a linear alkyl group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and n-hexyl (n-hexyl).
• Linear alkyl groups having 1 to 11 carbon atoms such as meta) acrylate, n-heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, or undecyl (meth) acrylate.
• alkyl (meth) acrylate having a branched alkyl group examples include s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, and isooctyl.
• Alkyl (meth) acrylate having a branched alkyl group having 1 to 11 carbon atoms such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate, isomyristyl (meth) acrylate.
• alkyl (meth) acrylates having a branched alkyl group having 12 to 30 carbon atoms such as isostearyl (meth) acrylate and decyltetradecanyl (meth) acrylate.
• alkyl (meth) acrylate having an alicyclic alkyl group examples include cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and terpene (meth). ) Acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned.
• Examples of the compound having a (meth) acryloyl group and an aromatic hydrocarbon group include benzyl (meth) acrylate and the like.
• Examples of the compound 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, and methoxypolypropylene glycol (meth) acrylate.
• Examples thereof include polybutylene glycol (meth) acrylate and methoxypolybutylene glycol (meth) acrylate.
• Examples of the compound having a (meth) acryloyl group and a group containing a heterocycle include tetrahydrofurfuryl (meth) acrylate and the like.
• 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 and the like.
• Examples of the compound having a (meth) acryloyl group and a group containing a silane group include 3-acryloyloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, and 10-methacryloyloxydecyl. Examples thereof include triethoxysilane, 10-acryloyloxydecyl triethoxysilane, and the like.
• Examples of the compound having a (meth) acryloyl group and a group containing a siloxane bond include silicone (meth) acrylate and the like.
• Examples of the compound having a (meth) acryloyl group and a halogen atom include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, and 1,1,1,3,3,3-hexafluoro.
• Examples of the compound having a (meth) acryloyl group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like.
• Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate.
• Acrylate examples thereof include hydroxyalkylcycloalkane (meth) acrylate such as (4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
• Examples of the compound 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, manufactured by Toa Synthetic Co., Ltd. Aronix M5400 "), 2-acryloyloxyethyl succinate (for example,” NK ester A-SA “manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
• Examples of the compound 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 the compound having a (meth) acryloyl group and an epoxy group include glycidyl (meth) acrylate, glycidyl ⁇ -ethyl (meth) acrylate, glycidyl ⁇ -n-propyl (meth) acrylate, and ⁇ -n-butyl.
• the content of other polymerizable compounds is, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50, based on the total amount of the composition. It may be 99% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70. It may be mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less.
• the content of the other polymerizable compound is, for example, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, and 50 parts by mass with respect to the total content of the polymerizable component of 100 parts by mass.
• it may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.
• 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 at preferably 105 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, and for example, 200 ° C. or lower, 190 ° C. or lower, or
• the composition may be cured by heating at 180 ° C. or lower.
• the heating time for heating the composition may be appropriately selected according to the composition of the composition so that the composition is suitably cured.
• thermal polymerization initiator examples include azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl, benzoyl peroxide, and excess.
• azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl, benzoyl peroxide, and excess.
• Lauroyl oxide di-t-butyl peroxide, di-t-hexyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t- Examples thereof include organic peroxides such as butylperoxy-3,3,5-trimethylcyclohexane and t-butylperoxyisopropyl carbonate.
• the thermal polymerization initiator may be used alone or in combination of two or more.
• the composition contains a photopolymerization initiator, for example, by irradiating the composition with light (for example, light containing at least a part of wavelengths of 200 to 400 nm (ultraviolet light)), a cured product of the composition is obtained.
• light for example, light containing at least a part of wavelengths of 200 to 400 nm (ultraviolet light)
• the light irradiation conditions may be appropriately set depending on the type of photopolymerization initiator.
• the photopolymerization initiator examples include a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an ⁇ -ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, and a photoactive oxime-based photopolymerization initiator.
• Benzoin-based photopolymerization initiator Benzyl-based photopolymerization initiator, benzophenone-based photopolymerization initiator, Ketal-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, acylphosphine oxide-based photopolymerization initiator, and the like. ..
• benzoin ether-based photopolymerization initiator examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, BASF).
• benzoin methyl ether examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, BASF).
• examples thereof include "Irgacure 651" manufactured by Anisole Methyl Ether and the like.
• acetophenone-based photopolymerization initiator examples include 1-hydroxycyclohexylphenyl ketone (for example, "Irgacure 184" manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2- (2-). Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (for example, "Irgacure 2959” manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one.
• methoxyacetophenone and the like can be mentioned.
• Examples of the ⁇ -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) -phenyl] -2-hydroxy-2-methylpropane-1-one, etc. Can be mentioned.
• Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride and the like.
• Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
• Examples of the benzoin-based photopolymerization initiator include benzoin and the like.
• Examples of the benzyl-based photopolymerization initiator include benzyl and the like.
• Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone and the like.
• Examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like.
• Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2, Examples thereof include 4-diisopropylthioxanthone and dodecylthioxanthone.
• acylphosphine-based photopolymerization initiator examples include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, and bis (2,).
• 6-Dimethoxybenzoyl) -n-butylphosphine oxide bis (2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1-methylpropane) -1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine oxide, Bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2-Methylpropan-1-yl) pho
• the above-mentioned photopolymerization initiator may be used alone or in combination of two or more.
• the content of the polymerization initiator is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, based on 100 parts by mass of the total content of the polymerizable component from the viewpoint of suitably advancing the polymerization. , More preferably 0.05 parts by mass or more.
• the content of the polymerization initiator is such that the molecular weight of the polymer in the cured product of the composition is in a suitable range, and from the viewpoint of suppressing decomposition products, the content of the polymerizable component is 100 parts by mass in total. It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.
• 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 phenol-based antioxidant, a benzophenone-based antioxidant, a benzoate-based antioxidant, a hindered amine-based antioxidant, a benzotriazole-based antioxidant, or the like, and preferably a phenol-based oxidation. It is an inhibitor.
• 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 of the positions of the ortho position with respect to the hydroxyl group in the phenol ring.
• the phenolic antioxidant has one or more such hindered phenol rings, preferably two or more, more preferably three or more, and even 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 based on the total amount of the composition, and is 10% by mass or less, 9% by mass or less, It may be 8% by mass or less, or 7% by mass or less.
• the composition can further contain other additives as needed.
• additives include, for example, plasticizers (eg, tack fire), fillers (eg, thermally conductive fillers), surface treatment agents (eg, silane coupling agents), dispersants, curing accelerators, colorants, crystal nuclei. Examples thereof include agents, heat stabilizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, flame retardant aids (for example, metal oxides) and the like.
• the content of the 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. from the viewpoint of further improving handleability.
• the composition may be solid at 25 ° C., in which case it is preferably liquid by heating (eg, at 50 ° C. or higher) from the viewpoint of further improving handleability.
• composition set a plurality of liquid type composition sets can be provided.
• the composition set according to one embodiment is a composition set including 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).
• the oxidizing agent and the reducing agent react to generate free radicals, and the polymerization of the polymerizable component such as the compound represented by the formula (1) proceeds.
• the 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 is obtained at a high speed.
• the first liquid preferably contains an oxidizing agent and a compound represented by the formula (1)
• the second liquid contains a reducing agent and a compound represented by the formula (1).
• the content of the compound represented by the formula (1) based on the total amount of the liquids constituting the composition set (for example, in the case of a two-component composition set, the total amount of the first liquid and the second liquid). May be the same as the range of the content of the compound represented by the formula (1) based on the total amount of the above-mentioned composition.
• 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.
• the organic peroxide may be, for example, hydroperoxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, diacyl peroxide or the like.
• the azo compound may be AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile) or the like.
• AIBN 2,2'-azobisisobutyronitrile
• V-65 azobisdimethylvaleronitrile
• 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.
• Examples thereof include (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, and di (3-methyl-3methoxybutylperoxy) dicarbonate.
• peroxyester examples include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t.
• Peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1,1-.
• dialkyl peroxide examples include ⁇ , ⁇ '-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and t-. Butylcumyl peroxide and the like can be mentioned.
• Diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, and dichloromethane peroxide. , Benzoyl peroxide, toluene, benzoyl peroxide and the like.
• the oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, and further preferably a 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 based on the total amount of the liquid constituting the composition set, and may be 10% by mass or less and 5% by mass. % 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.
• the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea and the like.
• the transition metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate and the like.
• the reducing agent may be used alone or in combination of two or more.
• the reducing agent is preferably a thiourea derivative or a transition metal salt from the viewpoint of excellent curing rate.
• the thiourea derivative may be, for example, ethylene thiourea.
• 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, based on the total amount of the liquid constituting the composition set, and may be 5% by mass or less. It may be 3% by mass or less, or 1% by mass or less.
• the composition set may further contain other polymerizable compounds and additives that can be used in the compositions described above. These components may be contained in one or both of the first liquid and the second liquid, and 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 the liquids constituting the composition set may be the same as the range of the contents of these components based on the total amount of the composition described above.
• the above-mentioned composition or composition set can realize low elasticity, high elongation and high strength in the cured product while having a low viscosity, so that it is used for a heat conductive material (also called a heat radiating material), an adhesive, and a structure. It is suitable for applications such as adhesives, battery binders, stress relaxation agents, sealants, coating agents, and paints.
• the cured product of the above-mentioned composition or the cured product of the mixture of the composition set is suitable for each of the above-mentioned applications because it can realize low elasticity, high elongation and high strength.
• a compound represented by the following formula (a-1) (a mixture having a weight average molecular weight of 1000 and x in the formula (a-1) being approximately an integer of approximately 21 ⁇ 3).
• a compound represented by the following formula (a-2) (a mixture having a weight average molecular weight of 700 and y in the formula (a-2) being an integer of approximately 11 ⁇ 3).
• a compound represented by the above formula (a-2) (a mixture having a weight average molecular weight of 4000 and y in the formula (a-2) being an integer of approximately 58 ⁇ 3).
• composition and cured product Each component was mixed at the compounding ratio shown in Table 1 to obtain each composition of Examples and Comparative Examples. Next, each of the compositions was filled in a 10 cm ⁇ 10 cm ⁇ 0.2 mm mold (made of SUS plate), covered with a SUS plate, and then heated and cured at 135 ° C. for 15 minutes to achieve a thickness. A cured product having a composition of 0.2 mm was obtained.

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