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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
  • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
• • 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
  • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
• • 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
  • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • 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
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
• • 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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2296—Oxides; Hydroxides of metals of zinc
• • 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
  • C08K3/28—Nitrogen-containing compounds
  • C08K2003/282—Binary compounds of nitrogen with aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives

Definitions

• the present invention relates to an ultraviolet-curing heat-dissipating resin composition that is excellent in printability, heat-dissipating properties, and adhesion to various substrates.
• the present invention also relates to a heat-dissipating pressure-sensitive adhesive sheet, a laminate, and a method for producing a laminate using the ultraviolet-curable heat-dissipating resin composition.
• Adhesives are used for bonding electronic components inside electronic devices such as smartphones and PCs.
• a general method of bonding using an adhesive first, an adhesive sheet having separators arranged on both sides of the adhesive is produced, and then the adhesive sheet is cut into a desired shape. After that, one separator is peeled off from the cut pressure-sensitive adhesive sheet, one surface of the exposed pressure-sensitive adhesive is bonded to the first adherend, and then the other separator is peeled off, The other surface of the exposed pressure-sensitive adhesive is laminated to the second adherend.
• a part of the pressure-sensitive adhesive sheet is discarded after cutting, resulting in waste. Moreover, air bubbles sometimes entered the bonding surface.
• Patent Document 1 discloses a radiation-curable pressure-sensitive adhesive composition that enables fine patterning and exhibits high adhesion to various adherends such as metals and plastics.
• a radiation-curable adhesive composition containing 10 to 70% by weight of an ethylenically unsaturated monomer containing no aromatic ring, 1 to 10% by weight of a photopolymerization initiator, and 10 to 55% by weight of a cross-linking agent as an invention of , the aromatic ring-free ethylenically unsaturated monomer contains 10 to 45% by weight of an alkyl (meth)acrylate having an alkyl group having 8 to 18 carbon atoms, and the crosslinking agent has a weight average molecular weight of 20,000 to 100,000.
• describes a radiation-curable adhesive composition containing 10 to 50% by weight of a urethane poly(meth)acrylate of
• Patent Document 2 discloses an invention for providing a photocurable adhesive composition that provides a laminate having an adhesive strength equivalent to that in the absence of oxygen even when irradiated with light in the presence of oxygen.
• a photocurable adhesive composition is described comprising a 150° C. tackifier and (F) a liquid plasticizer.
• the adhesive sheet may contain a filler.
• An invention of a flame-retardant, heat-conducting, electrically insulating, pressure-sensitive adhesive composition characterized by containing 0.0% by weight is disclosed.
• Patent Document 4 at least (a) a (meth)acrylic acid alkyl ester as a main component, a polar group-containing monomer, and a monomer component substantially free of a carboxyl group-containing monomer are copolymerized. and (b) a hydrated metal compound.
• JP 2013-216742 A WO2016/163152 JP-A-2004-59851 JP 2012-180495 A
• the present disclosure 1 comprises (A) a nitrogen-containing monomer, (B) a monofunctional (meth)acrylate monomer, (C) a cross-linking component, (D) a photopolymerization initiator, and (E) a thermal conductivity of 3 W/ and a thermally conductive filler of m ⁇ K or more, wherein the content of the (E) thermally conductive filler is 20 to 70% by volume, and the (E)
• the UV-curable heat-dissipating resin composition contains the nitrogen-containing monomer (A) in an amount of 10 to 35% by weight with respect to the total amount of the composition excluding the thermally conductive filler.
• the present disclosure 2 further includes the ultraviolet-curable heat-dissipating resin composition of the present disclosure 1, which further contains a non-reactive component that does not have reactivity with the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer. It is a thing.
• the non-reactive component is added in a ratio of 0.1 to 140 parts by weight with respect to 100 parts by weight of the total amount of the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer.
• 2 is an ultraviolet curable heat-dissipating resin composition of the present disclosure 2 containing.
• Present Disclosure 4 is the UV-curable heat-dissipating resin composition of Present Disclosure 2 or 3, wherein the non-reactive component contains at least one of a thermoplastic resin and a tackifier.
• Present Disclosure 5 is the ultraviolet-curable heat-dissipating resin composition according to any one of Present Disclosures 1 to 4, wherein the nitrogen-containing monomer (A) contains a monomer having a negative e value.
• the (C) crosslinking component has reactivity with the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer, or the (A) nitrogen-containing monomer, the (B) The UV-curable heat-dissipating resin composition according to any one of 2 to 5 of the present disclosure, which has reactivity with respect to the monofunctional (meth)acrylate monomer and the non-reactive component.
• the (C) cross-linking component has at least one bonding functional group selected from the group consisting of an isocyanate group, an epoxy group, an aldehyde group, a hydroxyl group, an amino group, a (meth)acrylate group, and a vinyl group.
• An ultraviolet curable heat-dissipating resin composition according to any one of 1 to 6 of the present disclosure.
• Present Disclosure 8 is the UV-curable heat-dissipating resin of any one of Present Disclosures 1 to 7, wherein the (C) cross-linking component contains a (meth)acrylate monomer having a gel fraction of 80% or more when homopolymerized. composition.
• the (C) crosslinking component is a (meth)acrylate monomer having a viscosity at 25° C.
• the present disclosure 10 is the present disclosure wherein the (E) thermally conductive filler is an inorganic filler containing at least one compound selected from the group consisting of metal oxides, metal hydroxides, metal nitrides, metal carbides, and metal borides. 10. The UV-curable heat-dissipating resin composition according to any one of 1 to 9.
• Present Disclosure 11 is the ultraviolet-curable heat-dissipating resin composition according to any one of Present Disclosures 1 to 10, which has a thermal conductivity of 0.30 W/m ⁇ K or more after curing.
• Present Disclosure 12 is the ultraviolet curable heat dissipation according to any one of Present Disclosures 1 to 11, further comprising 0.01 to 5.0% by weight of a dispersant with respect to 100% by weight of the (E) thermally conductive filler. It is a flexible resin composition.
• the content of the (D) photopolymerization initiator is 0.2 with respect to 100 parts by weight of the total amount of the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer. 13.
• present Disclosure 14 is a heat-dissipating pressure-sensitive adhesive sheet comprising a base material and a heat-dissipating pressure-sensitive adhesive layer comprising the UV-curable heat-dissipating resin composition of any one of Present Disclosures 1 to 13 provided on at least one side of the base material.
• Present Disclosure 15 is the heat dissipating adhesive sheet of Present Disclosure 14, wherein the heat dissipating adhesive layer is partially disposed on the substrate.
• the present disclosure 16 is a laminate in which a first adherend and a second adherend are bonded via the heat dissipating adhesive layer contained in the heat dissipating adhesive sheet of the present disclosure 14 or 15. .
• the present disclosure 17 is a first adherend, the UV-curable heat-dissipating resin composition of any one of the present disclosure 1 to 13 is applied and exposed to form a heat-dissipating adhesive layer, and the heat-dissipating A method for producing a laminate by attaching a second adherend onto an adhesive layer to produce a laminate.
• the method of applying the ultraviolet curable heat dissipation resin composition is inkjet printing, screen printing, spray coating, or spin coating, and the ultraviolet curable heat dissipation resin composition is the first 18 is a method of manufacturing a laminate of the present disclosure 17 that is partially applied onto an adherend.
• the present invention will be described in detail below.
• the inventors of the present invention have found that it is difficult to obtain sufficient reactivity to ultraviolet rays when a conventional pressure-sensitive adhesive composition is exposed without being covered with a separator during curing.
• the present inventors have found that when (E) a thermally conductive filler is filled in order to obtain heat dissipation, the ultraviolet transmittance is lowered, and thus the ultraviolet reactivity is further lowered. Therefore, as a result of repeated studies, by using a specific amount of (A) a nitrogen-containing monomer, a large amount of (E) a thermally conductive filler is added to ensure heat dissipation, and sufficient UV reactivity can be obtained. I found that it can be done.
• the ultraviolet-curable heat-dissipating resin composition contains (A) a nitrogen-containing monomer.
• the nitrogen-containing monomer is not particularly limited as long as it has a nitrogen atom in the molecule and a polymerizable group, but an amide compound having a vinyl group is preferable, and a cyclic amide compound having a vinyl group is more preferable.
• a compound having a lactam structure is more preferred.
• Examples of the amide compound having a vinyl group include N-vinylacetamide and (meth)acrylamide compounds.
• the (meth)acrylamide compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-hydroxyethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N -isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide and the like.
• Examples of the cyclic amide compound having a vinyl group include compounds represented by the following formula (1).
• n an integer of 2-6.
• Examples of the compound represented by formula (1) include N-vinyl-2-pyrrolidone and N-vinyl- ⁇ -caprolactam. Among them, N-vinyl- ⁇ -caprolactam is preferred.
• the nitrogen-containing monomer preferably contains a monomer having a negative e value.
• the content of the nitrogen-containing monomer (A) is 10 to 35% by weight with respect to the total amount of the composition excluding the thermally conductive filler (E). Even if the content of the nitrogen-containing monomer is 10% by weight or more, the coating film containing the thermally conductive filler is irradiated with ultraviolet rays in the presence of oxygen in which the upper surface of the coating is not covered with a separator. , sufficient UV reactivity can be obtained. When the content of the nitrogen-containing monomer is 35% by weight or less, the pressure-sensitive adhesive obtained has excellent adhesion to various substrates. A more preferable lower limit of the nitrogen-containing monomer content is 12% by weight, and a more preferable upper limit is 30% by weight.
• the ultraviolet-curable heat-dissipating resin composition contains (B) a monofunctional (meth)acrylate monomer.
• (meth)acrylic means acrylic or methacrylic
• the above "(meth)acrylate monomer” means a monomer having a (meth)acryloyl group
• the above “(meth)acryloyl ” means acryloyl or methacryloyl.
• the above-mentioned "monofunctional” means that one molecule of the monomer contains one (meth)acryloyl group.
• a monomer having a (meth)acryloyl group and nitrogen is treated as the nitrogen-containing monomer (A), not as the monofunctional (meth)acrylate monomer (B).
• Examples of the (meth)acrylate monomers include (meth)acrylic acid ester compounds and epoxy (meth)acrylates.
• (meth)acrylate means acrylate or methacrylate
• epoxy(meth)acrylate means that all epoxy groups in an epoxy compound react with (meth)acrylic acid. It represents a compound that has undergone
• Examples of the above (meth)acrylic acid ester compounds that are monofunctional include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.
• acrylates t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (me
• epoxy (meth)acrylate examples include bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, and caprolactone modified products thereof.
• the content of the (B) monofunctional (meth)acrylate monomer has a preferred lower limit of 20 parts by weight and a preferred upper limit of 70 parts by weight in 100 parts by weight of the total composition excluding the (E) thermally conductive filler. .
• the content of the monofunctional (meth)acrylate monomer is 20 parts by weight or more, the pressure-sensitive adhesive obtained has excellent adhesion to various substrates.
• the content of the monofunctional (meth)acrylate monomer is 70 parts by weight or less, the pressure-sensitive adhesive can be excellent in properties other than adhesion.
• a more preferable lower limit to the content of the monofunctional (meth)acrylate monomer is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.
• the ultraviolet-curable heat-dissipating resin composition contains (C) a cross-linking component.
• the cross-linking component is not particularly limited as long as it is a compound having two or more bonding functional groups in one molecule. or have reactivity with the (A) nitrogen-containing monomer, the (B) monofunctional (meth)acrylate monomer, and non-reactive components described later.
• the (C) crosslinking component preferably has at least one bonding functional group selected from the group consisting of isocyanate groups, epoxy groups, aldehyde groups, hydroxyl groups, amino groups, (meth)acrylate groups, and vinyl groups. Any material having these bonding functional groups can form cross-linked bonds with a sufficient density during curing.
• the cross-linking component (C) preferably contains a (meth)acrylate monomer having a gel fraction of 80% or more when homopolymerized.
• the (C) cross-linking component preferably comprises a (meth)acrylate monomer having a viscosity of 10000 cps or more at 25°C. Moreover, the (C) cross-linking component preferably contains a bifunctional (meth)acrylate monomer. By using such a (meth)acrylate monomer, the cohesive force of the UV-curable heat-dissipating resin composition is improved, and the printability of the composition and the adhesion of the resulting heat-dissipating adhesive layer are improved.
• (C) cross-linking component examples include radically polymerizable polyfunctional oligomers or monomers, polymers having cross-linkable functional groups, and the like.
• Examples of the radically polymerizable polyfunctional oligomer or monomer include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, and dipentaerythritol hexaacrylate.
• methacrylates similar to those described above may be used.
• Other examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylates, and methacrylates similar to those described above.
• These radically polymerizable polyfunctional oligomers or monomers may be used alone, or two or more of them may be used in combination.
• the content of the (C) cross-linking component is 0.1 to 0.1 in the total amount of 100% by weight of the (A) nitrogen-containing monomer, the (B) monofunctional (meth)acrylate monomer and the (C) cross-linking component. 25% by weight is preferred.
• the content of the cross-linking component (C) is within this range, the cohesive force of the ultraviolet-curable heat-dissipating resin composition is appropriately improved, and the printability of the composition and the heat-dissipating pressure-sensitive adhesive layer obtained are improved. Adhesion is improved.
• a more preferable lower limit for the content of the cross-linking component (C) is 0.5% by weight, and a more preferable upper limit is 15% by weight.
• the ultraviolet-curable heat-dissipating resin composition contains (D) a photopolymerization initiator.
• a photoradical polymerization initiator is preferably used as the photopolymerization initiator.
• a photoinitiator and a photoradical polymerization initiator may be used independently and may use 2 or more types together.
• radical photopolymerization initiator examples include benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
• alkylphenone compounds include acetophenone compounds.
• photoradical polymerization initiator examples include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-(dimethylamino)-1-(4-(morpholino)phenyl)-1-butanone, 2- (Dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one , bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy) -phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4, 6-trimethylbenzoyldiphenylphos
• the content of the photopolymerization initiator (D) is preferably a lower limit of 0.2 parts by weight with respect to 100 parts by weight of the total amount of the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer.
• the preferred upper limit is 10 parts by weight.
• a more preferable lower limit of the content of the photopolymerization initiator is 0.5 parts by weight, a more preferable upper limit is 3 parts by weight, a still more preferable upper limit is 2.5 parts by weight, and a particularly preferable upper limit is 2 parts by weight.
• content of a photoinitiator refers to the sum total of content of all the contained photoinitiators.
• the UV-curable heat-dissipating resin composition contains (E) a thermally conductive filler having a thermal conductivity of 3 W/m ⁇ K or more.
• the thermal conductivity of the (E) thermally conductive filler is not particularly limited, it is preferably 10 W/m ⁇ K or more, more preferably 20 W/m ⁇ K or more, and still more preferably 30 W/m ⁇ K or more.
• the thermal conductivity of the (E) thermally conductive filler is preferably high, so the upper limit is not particularly limited. It is about m ⁇ K.
• the material of the (E) thermally conductive filler is not particularly limited, and for example, carbides, nitrides, oxides, hydroxides, metals, carbonaceous materials, silicate minerals and the like can be used.
• the carbide include silicon carbide, boron carbide, aluminum carbide, titanium carbide, tungsten carbide, and the like.
• the nitride include silicon nitride, boron nitride, boron nitride nanotubes, aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, and lithium nitride.
• oxides examples include silicon oxide (silica), aluminum oxide (alumina) (including hydrates of aluminum oxide (boehmite, etc.)), magnesium oxide, titanium oxide, cerium oxide, zirconium oxide, and the like.
• oxides include transition metal oxides such as barium titanate, and metal ion-doped oxides such as indium tin oxide and antimony tin oxide.
• hydroxide examples include aluminum hydroxide, calcium hydroxide, magnesium hydroxide and the like.
• the metal include copper, gold, nickel, tin, iron, or alloys thereof.
• carbonaceous material include carbon black, graphite, diamond, graphene, fullerene, carbon nanotube, carbon nanofiber, nanohorn, carbon microcoil, nanocoil and the like.
• silicate minerals include talc.
• the (E) thermally conductive filler is preferably an inorganic filler containing at least one compound selected from the group consisting of metal oxides, metal hydroxides, metal nitrides, metal carbides and metal borides. Among them, alumina, aluminum hydroxide, aluminum nitride and zinc oxide are preferably used. By using these inorganic fillers, electrical insulation can be ensured while obtaining excellent thermal conductivity.
• the shape of the (E) thermally conductive filler is not particularly limited, and may be a spherical filler or a non-spherical filler.
• the thermally conductive filler may be used alone or in combination of two or more. From the viewpoint of effectively improving heat dissipation, two or more of different average particle sizes are used in combination. is preferred. More specifically, the thermally conductive fillers consist of a small particle size thermally conductive filler with an average particle size of 0.1 ⁇ m or more and 1.5 ⁇ m or less and a large particle size thermally conductive heat dissipating filler with an average particle size of more than 1.5 ⁇ m. and is preferably contained.
• the amount of the large particle size thermally conductive filler in the composition should be equal to or greater than the amount of the small particle size thermally conductive filler. is preferred.
• the amount of large particle size thermally conductive filler relative to the amount of small particle size thermally conductive filler is preferably 1 or more, and more It is preferably 1.5 or more, more preferably 2 or more, and particularly preferably 10 or less.
• the ultraviolet-curing heat-dissipating resin composition contains two or more types of thermally conductive fillers having different average particle sizes from the appearance of two or more peaks in the particle size distribution of the thermally conductive fillers.
• the content of the (E) thermally conductive filler is 20 to 70% by volume with respect to the total volume of the UV-curable heat-dissipating resin composition. When the content of the (E) thermally conductive filler is within this range, excellent thermal conductivity can be obtained.
• a more preferable lower limit of the content of the thermally conductive filler is 20% by volume, a more preferable upper limit is 65% by volume, a still more preferable lower limit is 30% by volume, and a further preferable upper limit is 60% by volume.
• the ultraviolet-curable heat-dissipating resin composition further contain a non-reactive component that does not have reactivity with the nitrogen-containing monomer (A) and the monofunctional (meth)acrylate monomer (B).
• a non-reactive component a compound that does not contain a reactive double bond or that does not substantially show polymerization reactivity even if it has a reactive double bond can be used.
• the cohesive force of the UV-curable heat-dissipating resin composition is improved, a thick coating film can be formed, and printability is excellent.
• the non-reactive component may exhibit reactivity to triggers such as heat and moisture after photopolymerization of the ultraviolet-curable heat-dissipating resin composition. It may be cured by heating with heat, or containing an isocyanate compound and cured by moisture, alcohol, or the like.
• the non-reactive component preferably contains at least one of a thermoplastic resin and a tackifier.
• thermoplastic resin examples include plasticizers such as organic esters, organic phosphates, and organic phosphites, and solvent-free acrylic polymers.
• plasticizer examples include organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Among them, an organic acid ester plasticizer is preferable. These plasticizers may be used alone or in combination of two or more.
• Examples of the organic acid esters include monobasic organic acid esters and polybasic organic acid esters.
• the monobasic organic acid ester is not particularly limited.
• monobasic organic acids such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and triethylene Glycol esters obtained by reaction with glycols such as glycol, tetraethylene glycol, tripropylene glycol and the like can be mentioned.
• the polybasic organic acid ester is not particularly limited. The obtained ester compound etc. are mentioned.
• organic acid esters include triethylene glycol-di-2-ethylbutyrate (3GH), triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol dicaprylate, triethylene glycol-di-n-octanoate, triethylene glycol-di-n-heptanoate (3G7) and the like.
• tetraethylene glycol-di-n-heptanoate (4G7), tetraethylene glycol-di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate , 1,3-propylene glycol di-2-ethylbutyrate and the like.
• 1,4-butylene glycol di-2-ethyl butyrate diethylene glycol-di-2-ethyl butyrate, diethylene glycol-di-2-ethylhexanoate, dipropylene glycol-di-2-ethyl butyrate, etc. mentioned.
• triethylene glycol di-2-ethylpentanoate tetraethylene glycol-di-2-ethylbutyrate (4GH), diethylene glycol dicapriate, dihexyl adipate (DHA), dioctyl adipate, hexylcyclohexyl adipate, diisononyl adipate, and heptyl nonyl adipate.
• DHA dihexyl adipate
• dioctyl adipate hexylcyclohexyl adipate
• diisononyl adipate diisononyl adipate
• heptyl nonyl adipate heptyl nonyl adipate.
• Other examples include oil-modified alkyds of sebacate, mixtures of phosphate esters and adipate esters, and mixed adipate esters made from alkyl alcohols having 4 to 9
• Examples of the organic phosphate or organic phosphite include compounds obtained by a condensation reaction between phosphoric acid or phosphorous acid and alcohol. Among them, a compound obtained by a condensation reaction between an alcohol having 1 to 12 carbon atoms and phosphoric acid or phosphorous acid is preferable.
• Examples of the alcohol having 1 to 12 carbon atoms include methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, and benzyl alcohol. mentioned.
• organic phosphate or organic phosphite examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tri(butoxyethyl) phosphate, tri(2-ethylhexyl) phosphite, isodecylphenyl phosphate, triisopropyl phosphate and the like.
• the solvent-free acrylic polymer for example, a polymer of at least one monomer selected from (meth)acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms, or the monomer and other and copolymers with copolymerizable monomers.
• examples of commercial products of the solvent-free acrylic polymer include ARUFON-UP1000 series, UH2000 series and UC3000 series manufactured by Toagosei Co., Ltd.
• tackifier examples include rosin-based resins and terpene-based resins.
• the rosin-based resin examples include rosin diol.
• the rosin diol is not particularly limited as long as it is a rosin-modified diol having two rosin skeletons and two hydroxyl groups in the molecule.
• a diol having a rosin component in the molecule is called a rosin polyol, and includes a polyether type such as polypropylene glycol (PPG) having a skeleton excluding the rosin component, a condensation polyester polyol, a lactone polyester polyol, There are polyester types such as polycarbonate diols.
• PPG polypropylene glycol
• polyester types such as polycarbonate diols.
• rosin diol examples include a rosin ester obtained by reacting a rosin with a polyhydric alcohol, an epoxy-modified rosin ester obtained by reacting a rosin with an epoxy compound, and a polyether having a rosin skeleton having a hydroxyl group. Modified rosin and the like can be mentioned. These can be produced by a conventionally known method.
• rosin component examples include abietic acid and its derivatives such as dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, diabietic acid, neoabietic acid, levopimaric acid and other pimaric acid type resin acids, and water obtained by hydrogenating these.
• examples include added rosin, disproportionated rosin obtained by disproportionating these, and the like.
• commercially available rosin-based resins include, for example, Pine Crystal D-6011, KE-615-3, KR-614, KE-100, KE-311, KE-359, KE-604 manufactured by Arakawa Chemical Industries, Ltd. and D-6250.
• terpene-based resin examples include terpene-phenol-based resins.
• the terpene phenol resin is a copolymer of phenol and a terpene resin, which is an essential oil component obtained from natural products such as pine resin and orange peel, and is obtained by hydrogenating at least a part of the copolymer. Also included are partially hydrogenated terpene phenolic resins or fully hydrogenated fully hydrogenated terpene phenolic resins.
• the fully hydrogenated terpene phenol-based resin is a terpene-based resin (tackifying resin) obtained by substantially completely hydrogenating a terpene phenol-based resin
• the partially hydrogenated terpene phenol-based resin is It is a terpene-based resin (tackifying resin) obtained by partially hydrogenating a terpene-phenolic resin.
• the terpene phenol-based resin has a terpene-derived double bond and a phenol-derived aromatic ring double bond.
• fully hydrogenated terpene phenolic resin means a tackifying resin in which both the terpene moiety and the phenolic moiety are completely or almost hydrogenated
• partially hydrogenated terpene phenolic resin refers to those It means a terpene phenolic resin in which the degree of hydrogenation at the site is not complete but partial.
• the hydrogenation method and reaction format are not particularly limited. Examples of commercially available terpene phenolic resins include YS Polystar NH (completely hydrogenated terpene phenolic resin) manufactured by Yasuhara Chemical Co., Ltd., and the like.
• the non-reactive component is preferably contained in a ratio of 0.1 to 140 parts by weight with respect to 100 parts by weight of the total amount of the (A) nitrogen-containing monomer and the (B) monofunctional (meth)acrylate monomer. .
• the content of the non-reactive component is within this range, the cohesive force of the ultraviolet-curable heat-dissipating resin composition is improved, a thick coating film can be formed, and the printability is excellent, and the It is also possible to suppress the decrease in adhesiveness.
• a more preferable lower limit for the content of the non-reactive component is 5 parts by weight, and a more preferable upper limit is 90 parts by weight.
• the dispersant is not particularly limited, and examples thereof include fatty acids, aliphatic amines, alkanolamides, phosphate esters, and the like.
• the above fatty acids are not particularly limited, and examples include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, coconut fatty acid; oleic acid, linoleic acid, linolenic acid, sorbic acid.
• beef tallow fatty acid castor hardened fatty acid and other unsaturated fatty acids.
• lauric acid, stearic acid, oleic acid and the like are preferable.
• the above-mentioned aliphatic amine is not particularly limited, and examples thereof include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl (coconut) amine, alkyl (hardened beef tallow) amine, alkyl (beef tallow) amine, and alkyl (soybean) amine. etc.
• the alkanolamide is not particularly limited, and examples thereof include coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.
• the phosphate is not particularly limited, and examples thereof include polyoxyethylene alkyl ether phosphate and polyoxyethylene alkyl allyl ether phosphate.
• the dispersant is preferably contained in an amount of 0.01 to 5.0% by weight with respect to 100% by weight of the thermally conductive filler (E).
• the content of the dispersant is within this range, the dispersibility of the thermally conductive filler (E) is improved, resulting in excellent printability.
• a more preferable lower limit to the content of the dispersant is 0.05% by weight, and a more preferable upper limit is 1% by weight.
• the ultraviolet-curable heat-dissipating resin composition may contain an antifoaming agent.
• the antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, acrylic polymer antifoaming agents, vinyl ether polymer antifoaming agents, and olefin polymer antifoaming agents.
• the ultraviolet curable heat-dissipating resin composition further contains a viscosity modifier, a silane coupling agent, a sensitizer, a thermosetting agent, a curing retarder, an antioxidant, a storage-stable Various known additives such as modifiers may be contained.
• the ultraviolet-curable heat-dissipating resin composition preferably does not substantially contain an organic solvent.
• the ultraviolet-curable heat-dissipating resin composition 100 It is preferable that the content of the organic solvent is 1% by weight or less.
• the UV-curable heat-dissipating resin composition preferably has a thermal conductivity of 0.30 W/m ⁇ K or more after curing. More preferably, it is 50 W/m ⁇ K or more.
• the viscosity of the ultraviolet curable heat-dissipating resin composition is not limited, it is preferably a paste having a viscosity of 0.1 to 500 Pa ⁇ s at 25° C. using an E-type viscometer.
• a more preferable lower limit of the viscosity is 1 Pa ⁇ s, and a more preferable upper limit is 450 Pa ⁇ s.
• the above viscosity is determined, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer, and using a cone plate of CP1 at a rotation speed of 1 to 100 rpm as appropriate from the optimum torque number in each viscosity region. can be measured by selecting
• the method for preparing the ultraviolet-curable heat-dissipating resin composition is not particularly limited.
• a mixer For example, using a mixer, (A) a nitrogen-containing monomer, (B) a monofunctional (meth)acrylate monomer, and (C ) a cross-linking component, (D) a photopolymerization initiator, (E) a thermally conductive filler, and, if necessary, additives and the like are mixed.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• the method of using the ultraviolet-curable heat-dissipating resin composition is not limited, it is suitable for printing. If a heat-dissipating adhesive layer is formed by applying a desired pattern on an adherend (base material) by printing, the adhesive in a desired shape is obtained by cutting the sheet-like adhesive immediately before lamination. Compared to , there is an advantage that cutting work can be omitted. As a result, it is possible to suppress the generation of waste and reduce the environmental load.
• the printing method is not particularly limited, and includes screen printing, inkjet printing, gravure printing, etc. Among them, screen printing is preferably used.
• the above ultraviolet-curable heat-dissipating resin composition forms a heat-dissipating adhesive layer by curing with ultraviolet irradiation.
• a heat-dissipating adhesive layer may be formed directly on the adherend.
• the method of forming the heat-dissipating adhesive layer directly on the adherend can minimize the number of times of bonding and prevent air bubbles from entering the interface during bonding.
• the method of forming the heat-dissipating adhesive layer on the base material (separator) has the advantage that the heat-dissipating adhesive layer is placed on the adherend by transfer, so that there are few restrictions in construction.
• the heat-dissipating pressure-sensitive adhesive sheet, the laminate, and the method for producing the laminate using the ultraviolet-curable heat-dissipating resin composition will be described below.
• a heat-dissipating pressure-sensitive adhesive sheet comprising a base material and a heat-dissipating pressure-sensitive adhesive layer made of the ultraviolet-curable heat-dissipating resin composition of the present invention provided on at least one side of the base material is also one aspect of the present invention.
• a resin film is preferably used.
• Materials for the resin film include, for example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene and acrylonitrile-styrene copolymers. Examples include styrene-based polymers such as (AS resin), polycarbonate-based polymers, and the like.
• Materials for the transparent protective film include polyethylene, polypropylene, polyolefins having a cyclo- or norbornene structure, polyolefin-based polymers such as ethylene/propylene copolymers, vinyl chloride-based polymers, and amide-based polymers such as nylon and aromatic polyamides.
• imide-based polymer imide-based polymer, sulfone-based polymer, polyethersulfone-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, acrylate-based polymer, polyoxymethylene-based polymer
• the thickness of the base material is not particularly limited, and is, for example, about 1 to 500 ⁇ m.
• the base material is preferably subjected to release treatment so that the heat-dissipating adhesive layer can be easily peeled off after being attached to the adherend.
• release-treated polyethylene terephthalate (PET) sheet is preferably used.
• the heat-dissipating pressure-sensitive adhesive layer can be formed by applying the ultraviolet-curable heat-dissipating resin composition and then curing the composition by irradiating it with ultraviolet rays. It is preferable that the heat-dissipating adhesive layer is partially disposed on the substrate by a method such as printing.
• the thickness of the heat-dissipating adhesive layer is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more. When the thickness of the heat-dissipating adhesive layer is 50 ⁇ m or more, sufficient adhesion can be obtained, and heat can be diffused and transferred. Although the upper limit of the thickness of the heat-dissipating adhesive layer is not particularly limited, it is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, from the viewpoint of responding to thinning of electronic devices.
• one surface (the side not in contact with the base material) of the heat-dissipating pressure-sensitive adhesive layer is attached to a first adherend, and then the base material is peeled off to expose the heat-dissipating adhesive sheet.
• a laminate can be produced by bonding the other surface of the adhesive layer to a second adherend. Examples of materials for the first adherend and the second adherend include metals such as stainless steel and aluminum, and resins.
• One of the first adherend and the second adherend is an electronic component that emits heat such as a power semiconductor chip, and the other of the first adherend and the second adherend is for heat dissipation. It is preferably a member.
• a laminate in which a first adherend and a second adherend are laminated via the heat-dissipating adhesive layer contained in the heat-dissipating pressure-sensitive adhesive sheet of the present invention is also one aspect of the present invention. .
• the ultraviolet curable heat-dissipating resin composition of the present invention is applied onto the first adherend and exposed to light to form a heat-dissipating adhesive layer, and a second adherend is formed on the heat-dissipating adhesive layer.
• a method for producing a laminate, in which a laminate is produced by sticking, is also one aspect of the present invention. Inkjet printing, screen printing, spray coating, or spin coating is preferably used as a method for applying the ultraviolet-curable heat-dissipating resin composition. Moreover, it is preferable that the ultraviolet-curable heat-dissipating resin composition is partially applied onto the first adherend.
• an ultraviolet-curable heat-dissipating resin composition that is excellent in printability, heat-dissipating properties, and adhesion to various substrates. Further, according to the present invention, it is possible to provide a heat-dissipating pressure-sensitive adhesive sheet, a laminate, and a method for producing a laminate using the ultraviolet-curable heat-dissipating resin composition.
• Examples 1 to 20 Comparative Examples 1 to 8> According to the compounding ratios shown in Tables 1 and 2, each material was mixed with a planetary stirrer (Thinky Co., Ltd. "Awatori Mixer") to prepare the ultraviolet-curable heat-dissipating resin compositions of Examples and Comparative Examples. Obtained.
• the details of the materials indicated by abbreviations in the table are as follows. Details of the thermally conductive filler are shown in Table 3.
• NVC N-vinyl- ⁇ -caprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
• ACMO acryloyl morpholine (manufactured by KJ Chemical)
• DMAA dimethylacrylamide (manufactured by KJ Chemical Co., Ltd.)
• IDAA isodecyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• 4HBA 4-hydroxybutyl acrylate (manufactured by Mitsubishi Chemical Corporation)
• CN9004 urethane (bifunctional, manufactured by Sartomer Japan, "CN9004")
• EB3700 Bisphenol A type epoxy acrylate (bifunctional, manufactured by Daicel Allnex, "EBECRYL 3700")
• TPO Omnirad TPO H (manufactured by IGM Resins BV) 819: Omnirad 819 (manufactured by IGM Resins BV)
• EBECRYL 3700 Bis
• An acrylic polymer as a thermoplastic resin used in Examples and Comparative Examples was prepared by the following method. 100 parts by weight of 2-ethylhexyl acrylate, 3 parts by weight of acrylic acid, 0.1 part by weight of 2-hydroxyethyl acrylate, and 0.1 part by weight of 2-hydroxyethyl acrylate were placed in a 2 L separable flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. 300 parts by weight of ethyl acetate were added. Next, after nitrogen gas was blown in for 30 minutes to replace the inside of the reaction vessel with nitrogen, the inside of the reaction vessel was heated to 80° C. while stirring.
• the resulting solution was diluted with a diluting solvent (a mixed solvent of methanol and toluene, the weight ratio of methanol and toluene being 1:2) to obtain a solution with a solid content of 20% by weight.
• a diluting solvent a mixed solvent of methanol and toluene, the weight ratio of methanol and toluene being 1:2
• this solution was applied onto a release-treated PET film so that the thickness after drying was 100 ⁇ m, and dried at 80° C. for 1 hour and 110° C. for 1 hour to obtain an acrylic polymer. .
• the said cured material used for evaluation was produced as follows. (Production of cured product)
• the UV-curable heat-dissipating resin composition was applied with an applicator to a thickness of 150 ⁇ m on a PET sheet (“1-E” manufactured by Nippa Co., Ltd., thickness 50 ⁇ m) that had been subjected to a release treatment on one side.
• an LED curing device (“GUC-584M” manufactured by Group-up) was used in an atmospheric environment to set the UV illuminance to 300 mW/cm 2 at a wavelength of 365 nm, By irradiating ultraviolet rays with an irradiation energy of 900 mJ/cm 2 , the ultraviolet-curable heat-dissipating resin composition was cured to obtain a cured product.
• Thermal conductivity The cured product of the UV-curable heat-dissipating resin composition was cut into a size of 5 cm x 10 cm, and measured at an ambient temperature of 23°C ⁇ 2°C using a rapid thermal conductivity meter (“QTM500” manufactured by Kyoto Electronics Industry Co., Ltd.). was used to measure the thermal conductivity.
• QTM500 rapid thermal conductivity meter
• Dispensing Applicability Dispensing device (“SHOTMASTER-300” manufactured by Musashi Engineering Co., Ltd.) was used to apply a coating having a thickness of 100 ⁇ m and a width of 1000 ⁇ m, and a cured product was obtained by irradiating ultraviolet rays in the same manner as described above. State of the cured product. was observed and evaluated according to the following criteria.
• the crimped test piece was subjected to 180° peeling at a speed of 300 mm/min using a universal testing machine (“Tensilon RTI-1310” manufactured by A AND D). Room-temperature adhesive strength was measured using a test piece adjusted to 25°C. Adherence at room temperature was measured for adherends made of two materials, Cu and Al, and evaluated according to the following criteria. [Evaluation criteria] ⁇ : 5 N / inch or more ⁇ : 3 N / inch or more, less than 5 N / inch ⁇ : 1.5 N / inch or more, less than 3 N / inch ⁇ : less than 1.5 N / inch (cannot be pasted)
• An ultraviolet curable heat-dissipating resin composition is screen-printed on an aluminum plate, and an LED curing device (manufactured by Group-up, "GUC-584M") is used so that the UV illumination at a wavelength of 365 nm is 300 W/cm 2 .
• an LED curing device manufactured by Group-up, "GUC-584M”
• the ultraviolet-curable heat-dissipating resin composition was cured to obtain a cured product.
• the cured product was attached to the back surface of the FR4 substrate. After that, voltage was applied to the chip resistor under the same conditions so as to obtain the rated power, and after 5 minutes, the temperature (Y) of the hot spot was measured by thermography.
• Hot spot reduction rate (%) Y/X*100 [Evaluation criteria] ⁇ : Hot spot reduction rate less than 100% ⁇ : Hot spot reduction rate 100% or more
• an ultraviolet-curable heat-dissipating resin composition that is excellent in printability, heat-dissipating properties, and adhesion to various substrates. Further, according to the present invention, it is possible to provide a heat-dissipating pressure-sensitive adhesive sheet, a laminate, and a method for producing a laminate using the ultraviolet-curable heat-dissipating resin composition.

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• 2022
  • 2022-05-30 WO PCT/JP2022/021984 patent/WO2022255317A1/ja not_active Ceased
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