CN104487531A - Heat-conductive adhesive sheet - Google Patents
Heat-conductive adhesive sheet Download PDFInfo
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- CN104487531A CN104487531A CN201380038685.2A CN201380038685A CN104487531A CN 104487531 A CN104487531 A CN 104487531A CN 201380038685 A CN201380038685 A CN 201380038685A CN 104487531 A CN104487531 A CN 104487531A
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- methyl
- thermal conductivity
- monomer
- conductive adhesive
- adhesive sheet
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
-
- 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
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid 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
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/28—Metal sheet
-
- 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
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Abstract
A heat-conductive adhesive sheet is provided with a metal layer and a heat-conductive adhesive agent layer laminated on at least one surface of the metal layer. The heat-conductive adhesive agent layer contains: an adhesive component that is produced by polymerizing a monomer component comprising a (meth)acrylic acid alkyl ester; and heat-conductive particles. The monomer component contains substantially no carboxyl-group-containing monomer.
Description
Technical field
The present invention relates to thermal conductivity adhesive sheet, specifically, relate to and needing the suitable thermal conductivity adhesive sheet used in thermal conductivity and both industrial field fusible.
Background technology
In the past, knownly in the heat radiation of various equipment, thermal conductivity sheet is used.
Such as, in organic EL light emitting device, propose and utilize acrylic adhesive tape by bonding with the stacked body of organic light emission (for example, referring to following patent documentation 1 for the thermal diffusion sheet be made up of graphite flake.)。
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-119237 publication
Summary of the invention
The problem that invention will solve
But, because the graphite flake proposed in patent documentation 1 is hard and crisp, therefore exist when sharp processing to produce and break or defect, the unfavorable condition of bending process of maybe can not carrying out.
In order to eliminate above-mentioned unfavorable condition, also discuss and use the tinsel such as aluminium foil, Copper Foil to replace graphite flake, now, because the carboxyl (acidic group) comprised in acrylic adhesive tape causes the surface oxidisation (corrosion) in tinsel, therefore, there is the unfavorable condition that degraded appearance or the reliability of equipment of being fitted by acrylic adhesive tape further reduce.
Further, in the structure proposed in patent documentation 1, there is the unfavorable condition that the thermal conductivity in direction, face (direction orthogonal with thickness direction) is insufficient.
The object of the present invention is to provide processibility and operability excellence, outward appearance is also excellent simultaneously, and the heat conductive adhesive sheet of the direction excellence orthogonal with thickness direction.
Solve the means of problem
The heat conductive adhesive layer that thermal conductivity adhesive sheet of the present invention possesses metal level and folds at least one surface layer of described metal level, described heat conductive adhesive layer contains the adhesive composition and thermal conductivity particle that obtain by making the polymerizing monomer components containing (methyl) alkyl acrylate, and described monomer component is not in fact containing carboxylic monomer.
In addition, in thermal conductivity adhesive sheet of the present invention, the monomer of preferred described monomer component also containing amide-containing.
In addition, the thermal conductivity in the direction that thermal conductivity adhesive sheet of the present invention is preferably orthogonal with thickness direction is more than 20W/mK.
In addition, when thermal conductivity adhesive sheet of the present invention preferably preserves 1000 hours under the atmosphere of temperature 85 DEG C, relative humidity 85%, do not corrode in the described one side of described metal level.
Invention effect
Thermal conductivity adhesive sheet of the present invention is owing to possessing metal level, and therefore processibility and operability are excellent.
In addition, thermal conductivity adhesive sheet also possesses at the folded heat conductive adhesive layer of at least one surface layer of metal level, and heat conductive adhesive layer contains the adhesive composition and thermal conductivity particle that obtain by making the polymerizing monomer components containing (methyl) alkyl acrylate.Therefore, if heat conductive adhesive layer is bonded to heat release object, then the heat produced by heat release object is by containing the heat conductive adhesive layer of thermal conductivity particle to metal layer conductive, then, along metal level, that is, effectively conduct to the direction orthogonal with thickness direction.While heat conduction in above-mentioned metal level, in heat conductive adhesive layer, from heat release object produce heat also along heat conductive adhesive layer, that is, effectively conduct to the direction orthogonal with thickness direction.
Therefore, the excellent thermal conductivity of the above-mentioned orthogonal directions of thermal conductivity adhesive sheet.
Further, because monomer component is not in fact containing carboxylic monomer, therefore can prevent from resulting from least one side of metal level the generation of the corrosion of carboxyl.Therefore, good outward appearance can be guaranteed, prevent the reduction of the reliability of the equipment configured.
Accompanying drawing explanation
Fig. 1 is the sectional view of the embodiment representing thermal conductivity adhesive sheet of the present invention.
Embodiment
Fig. 1 represents the sectional view of an embodiment of thermal conductivity adhesive sheet of the present invention.
In FIG, thermal conductivity adhesive sheet 1 possesses metal level 2 and heat conductive adhesive layer 3.
Metal level 2 is formed as the tabular (foil-like) with the outer shape same shape of thermal conductivity adhesive sheet 1.As the metal forming metal level 2, such as copper, silver, gold, iron, chromium, nickel, aluminium, iron or their alloy (stainless steel, copper-beryllium, phosphor bronze, iron-nickel etc.) etc. can be enumerated.Can preferably enumerate copper, aluminium.
The thickness of metal level 2 is such as more than 1 μm, is preferably more than 10 μm, in addition, such as, is less than 1000 μm, is preferably less than 100 μm.
In addition, the thermal conductivity of direction, the face PD of metal level 2 is such as more than 50W/mK, and be preferably more than 100W/mK, being more preferably more than 200W/mK, in addition, is also below 1000W/mK.Thermal conductivity is described in detail in the evaluation of the embodiment below.
Heat conductive adhesive layer 3 has thermal conductivity and binding property (pressure-sensitive adhesive) concurrently, is laminated in the whole back side (face of thickness direction) of metal level 2.Heat conductive adhesive layer 3 is containing adhesive composition and thermal conductivity particle.
Adhesive composition obtains by making polymerizing monomer components.
Monomer component contains (methyl) alkyl acrylate is as principal constituent.
(methyl) alkyl acrylate is alkyl methacrylate and/or alkyl acrylate, can enumerate such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) vinylformic acid nonadecyl ester, the moieties such as (methyl) vinylformic acid eicosyl ester are (methyl) alkyl acrylate of the alkyl of the C1-20 of straight-chain or branched.
In these (methyl) alkyl acrylates, particularly from the balance aspect easily obtaining adhesion properties, preferably can list (methyl) vinylformic acid C2-12 alkyl ester, more preferably can list (methyl) vinylformic acid C4-9 alkyl ester.
(methyl) alkyl acrylate such as with more than 60 quality %, preferably with more than 80 quality %, such as, coordinates with the ratio of below 99 quality % in monomer component.
As monomer component, the monomer etc. of the monomer of amide-containing, energy copolymerization also can be listed further.
The monomer of amide-containing is that containing amide moieties, (-CO-NR-, R represent hydrogen atom or alkyl in molecule.) acid amides system monomer, such as N-(methyl) acryloyl morpholine can be enumerated, ring-type (methyl) acrylamides such as N-(methyl) acryl tetramethyleneimine, such as (methyl) acrylamide, N-replaces (methyl) acrylamide (such as, N-ethyl (methyl) acrylamide, N-alkyl (methyl) acrylamides such as N-normal-butyl (methyl) acrylamide, such as N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-bis-(normal-butyl) (methyl) acrylamide, N, N-dialkyl group (methyl) acrylamides such as N, N-bis-(tertiary butyl) (methyl) acrylamide) etc. non-annularity (methyl) acrylamide, such as NVP (NVP), N-vinyl-2-piperidone, N-vinyl-3-morpholone mai, N-vinyl-2-hexanolactam, N-vinyl-1,3-oxazine-2-ketone, the N-vinyl cyclic acid amides such as N-vinyl-3,5-morpholine diketone, such as N-N-cyclohexylmaleimide, the monomer containing maleimide skeleton such as N-phenylmaleimide, such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-2-ethylhexyl clothing health imide, N-lauryl clothing health imide, the clothing health imide series monomers such as N-cyclohexyl clothing health imide, such as N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxygen hexa-methylene succinimide, the succinimide system monomers such as N-(methyl) acryl-8-oxygen hexa-methylene succinimide, such as N-(2-hydroxyethyl) (methyl) acrylamide (HEAA/HEMA), N-(2-hydroxypropyl) (methyl) acrylamide, N-(1-hydroxypropyl) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide, N-(2-hydroxybutyl) (methyl) acrylamide, N-(3-hydroxybutyl) (methyl) acrylamide, N-hydroxyalkyl (methyl) acrylamides such as N-(4-hydroxybutyl) (methyl) acrylamide.
In the monomer of amide-containing, preferably can list N-vinyl cyclic acid amides, N-hydroxyalkyl (methyl) acrylamide.
The monomer of amide-containing can be used alone or two or more and use, preferably and use.Can specifically list N-vinyl cyclic acid amides and N-hydroxyalkyl (methyl) acrylamide and use.
The monomer of amide-containing such as with below 20 quality %, preferably with below 15 quality %, more preferably with below 10 quality %, in addition, such as, coordinates with the ratio of more than 1 quality % in monomer component.
In addition, and during with N-vinyl cyclic acid amides and N-hydroxyalkyl (methyl) acrylamide, N-vinyl cyclic acid amides in monomer component such as with below 15 quality %, preferably with below 10 quality %, more preferably with below 8 quality %, in addition, such as coordinate with the ratio of more than 5 quality %, in addition, N-hydroxyalkyl (methyl) acrylamide in monomer component such as with below 5 quality %, preferably with below 4 quality %, more preferably with below 3 quality %, in addition, such as coordinate with the ratio of more than 0.5 quality %.
By comprising the monomer of amide-containing in monomer component, excellent binding property (pressure-sensitive adhesive) can be given to heat conductive adhesive layer 3.
Can the monomer of copolymerization be can with the monomer of above-mentioned monomer (monomer of (methyl) alkyl acrylate and/or amide-containing) copolymerization.As the monomer of such energy copolymerization, (methyl) glycidyl acrylate can be enumerated such as, allyl glycidyl ether etc. contain the monomer of epoxy group(ing), such as (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) methoxyethyl glycol ester, (methyl) methoxyethyl polypropylene glycol esters etc. contain the monomer of alkoxyl group, (methyl) alkali metal salts of acrylic acids such as such as (methyl) sodium acrylate, such as vinyl cyanide, the monomer of the cyano-containings such as methacrylonitrile, such as vinylbenzene, the styrenic monomers such as alpha-methyl styrene, such as ethene, propylene, isoprene, divinyl, the alpha-olefins such as iso-butylene, such as vinylformic acid 2-isocyanatoethyl ester, methacrylic acid 2-isocyanatoethyl esters etc. contain the monomer of isocyanato, such as vinyl-acetic ester, the vinyl ester system monomers such as propionate, the vinyl ether system monomers such as such as alkyl vinyl ether, such as (methyl) vinylformic acid tetrahydro furfuryl esters etc. are containing (methyl) acrylate of heterocycle, the monomer of the halogen atoms such as such as (methyl) fluoroalkyl base ester, such as 3-(methyl) acryloxypropyl Trimethoxy silane, vinyltrimethoxy silanes etc. containing the monomer of alkoxysilyl, such as, contain the monomer of the silicone-containing skeletons such as the silicone of (methyl) acryl, such as (methyl) vinylformic acid cyclopropyl ester, (methyl) vinylformic acid cyclobutyl ester, (methyl) vinylformic acid cyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid suberyl ester, (methyl) vinylformic acid ring octyl group ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate etc. contain (methyl) acrylate of ester ring type alkyl, such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) phenoxy ethyl acrylate, (methyl) vinylformic acid phenoxy group binaryglycol esters etc. are containing (methyl) acrylate etc. of aromatic hydrocarbyl.
The monomer of energy copolymerization can be used alone or and use.
In the monomer of these energy copolymerization, preferably can list the monomer containing alkoxyl group.
The monomer of energy copolymerization such as with below 30 quality %, preferably with below 20 quality %, more preferably with below 15 quality %, in addition, such as, with more than 5 quality %, preferably coordinates with the ratio of more than 10 quality % in monomer component.
In addition, monomer component such as can also in the proper ratio containing containing sulfo group monomer, have the monomer of nitrogen-sulfo group concurrently, have the monomer (not comprising carboxylic monomer described later) containing polar group such as monomer of hydroxyl-phosphate concurrently.
As the monomer containing sulfo group, such as styrene sulfonic acid, allyl sulphonic acid, (methyl) vinylformic acid sulfopropyl ester, (methyl) propane sulfonic acid etc. can be enumerated.As the monomer having nitrogen-sulfo group concurrently, such as 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid etc. can be enumerated.As the monomer having hydroxyl-phosphate concurrently, (methyl) acryl phosphoric acid 2-hydroxyethyl ester etc. can be enumerated such as.
On the other hand, monomer component is not containing carboxylic monomer.That is, the monomer containing polar group does not contain carboxylic monomer.
In carboxylic monomer, comprise (methyl) vinylformic acid (MA/AA), methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid etc., also comprise the such as carboxylic acid anhydride such as maleic anhydride, itaconic anhydride further, such as (methyl) vinylformic acid carboxyalkyl such as (methyl) vinylformic acid carboxy ethyl ester, (methyl) vinylformic acid carboxy pentyl ester ester etc.If monomer component containing carboxylic monomer, then causes the back side of metal level 2 to be corroded by carboxyl (acidic group), outward appearance reduces.
Adhesive composition containing proportional be such as below 50 quality % relative to heat conductive adhesive layer 3, be preferably below 35 quality %, being more preferably below 30 quality %, in addition, such as, is also more than 10 quality %, be preferably more than 20 quality %.
Thermal conductivity particle is formed with granular by thermally conductive materials, as such thermally conductive materials, can enumerate such as hydrated metal compound.
The kick off temperature of hydrated metal compound is the scope of 150 ~ 500 DEG C, is by formula M
xo
ynH
2o (M is atoms metal, x, y be by the valency of metal determine more than 1 integer, n is the number containing crystal water) compound that represents or the double salt comprising above-claimed cpd.
As hydrated metal compound, such as aluminium hydroxide [Al can be enumerated
2o
33H
2o; Or Al (OH)
3], boehmite [Al
2o
3h
2o; Or AlOOH], magnesium hydroxide [MgOH
2o; Or Mg (OH)
2], calcium hydroxide [CaOH
2o; Or Ca (OH)
2], zinc hydroxide [Zn (OH)
2], silicic acid [H
4siO
4; Or H
2siO
3; Or H
2si
2o
5], ironic hydroxide [Fe
2o
3h
2o or 2FeO (OH)], copper hydroxide [Cu (OH)
2], hydrated barta [BaOH
2o; Or BaO9H
2o], Zirconium oxide hydrate [ZrOnH
2o], tin oxide hydrate [SnOH
2o], alkaline magnesium carbonate [3MgCO
3mg (OH)
23H
2o], hydrotalcite [6MgOAl
2o
3h
2o], dawsonite [Na
2cO
3al
2o
3nH
2o], borax [Na
2oB
2o
55H
2o], zinc borate [2ZnO3B
2o
53.5H
2o] etc.
In addition, as thermally conductive materials, except above-mentioned hydrated metal compound, also can enumerate such as boron nitride, aluminium nitride, silicon nitride, gan, silicon carbide, silicon-dioxide, aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, stannic oxide, cupric oxide, nickel oxide, metaantimmonic acid doped stannum oxide, calcium carbonate, barium titanate, potassium titanate, copper, silver, gold, nickel, aluminium, platinum, carbon (comprising diamond) etc.
As thermally conductive materials, from the reason of heat conductive adhesive layer 3 being given to high thermal conductivity and flame retardant resistance, preferably can list hydrated metal compound, more preferably can list aluminium hydroxide.
Such as, as long as the shape of thermal conductivity particle is just not particularly limited for granular (Powdered), can be bulk, needle-like, tabular, stratiform.Bulk comprises such as spherical, rectangular shape, broken shape or theirs is irregularly shaped.
The size of thermal conductivity particle is not particularly limited, such as 1 median size, be such as more than 0.1 μm, be preferably more than 0.5 μm, be more preferably more than 0.7 μm, more preferably more than 1 μm, in addition, such as, be also less than 1000 μm, be preferably less than 200 μm, being more preferably is less than 100 μm, more preferably less than 80 μm.1 particle diameter of thermal conductivity particle, based on the size-grade distribution measured by the particle size distribution method in laser scattering method, as the median size of volume reference, more specifically, is obtained as D50 value (accumulating 50% median particle diameter).
These thermal conductivity particles are at commercial type, such as, as the thermal conductivity particle comprising aluminium hydroxide, trade(brand)name " Higilite H-100-ME " (Showa electrician Inc.) can be enumerated, trade(brand)name " HigiliteH-10 " (Showa electrician Inc.), trade(brand)name " Higilite H-32 " (Showa electrician Inc.), trade(brand)name " Higilite H-31 " (Showa electrician Inc.), trade(brand)name " Higilite H-42 " (Showa electrician Inc.), trade(brand)name " Higilite H-43M " (Showa electrician Inc.), trade(brand)name " B103ST " (Japanese light metal Inc.) etc., such as, as the thermal conductivity particle comprising magnesium hydroxide, trade(brand)name " KISUMA 5A " (consonance chemical industrial company system) etc. can be enumerated.
In addition, as the thermal conductivity particle comprising boron nitride, trade(brand)name " HP-40 " (Shui Dao alloy iron Inc.) can be enumerated, trade(brand)name " PT620 " (Mai Tu Inc.) etc., such as, as the salic thermal conductivity particle of bag, trade(brand)name " AS-50 " (Showa electrician Inc.) can be enumerated, trade(brand)name " AS-10 " (Showa electrician Inc.) etc., such as, as the thermal conductivity particle comprising metaantimmonic acid doped stannum oxide, trade(brand)name " SN-100S " (stone originates in industry Inc.) can be enumerated, trade(brand)name " SN-100P " (stone originates in industry Inc.), trade(brand)name " SN-100D (water-dispersion product) " (stone originates in industry Inc.) etc., such as, as the thermal conductivity particle comprising titanium oxide, trade(brand)name " TTO series " (stone originates in industry Inc.) etc. can be enumerated, such as, as the thermal conductivity particle comprising zinc oxide, trade(brand)name " SnO-310 " (Osaka, Sumitomo cement company system) can be enumerated, trade(brand)name " SnO-350 " (Osaka, Sumitomo cement company system), trade(brand)name " SnO-410 " (Osaka, Sumitomo cement company system) etc.
These thermal conductivity particles can be used alone or and with different multiple mutually.
Thermal conductivity particle containing proportional relative to adhesive composition 100 mass parts such as lower than 500 mass parts, be preferably below 450 mass parts, be more preferably below 400 mass parts, more preferably below 350 mass parts, in addition, such as, be also more than 1 mass parts, be preferably more than 10 mass parts, be more preferably more than 100 mass parts, more preferably more than 200 mass parts.
In addition, thermal conductivity particle containing proportional be such as more than 50 quality % relative to heat conductive adhesive layer 3, be preferably more than 65 quality %, being more preferably more than 70 quality %, such as, is also below 90 quality %, be preferably below 80 quality %.
If the mixing ratio of thermal conductivity particle is in above-mentioned scope, then can give excellent thermal conductivity and excellent binding property (pressure-sensitive adhesive) to heat conductive adhesive layer 3.
Then, the method manufacturing heat conductive adhesive layer 3 is described.
In order to manufacture heat conductive adhesive layer 3, such as, first, adhesive composition, the adhesive composition prepared and thermal conductivity particle is prepared.In addition, also can disposable cooperation adhesive composition and thermal conductivity particle.
Further, also coordinating containing after for the formation of the monomer composition of the monomer component of adhesive composition and thermal conductivity particle, polymerizing monomer components can be made.
After preferred cooperation monomer composition and thermal conductivity particle, make polymerizing monomer components.
In order to prepare monomer composition, first, in above-mentioned monomer component, polymerization starter is coordinated.
As polymerization starter, such as Photoepolymerizationinitiater initiater, thermal polymerization can be enumerated.
As Photoepolymerizationinitiater initiater, such as benzoin ether system Photoepolymerizationinitiater initiater, methyl phenyl ketone system Photoepolymerizationinitiater initiater, α-one alcohol system Photoepolymerizationinitiater initiater, aromatic sulfonyl system Photoepolymerizationinitiater initiater, photolytic activity oxime system Photoepolymerizationinitiater initiater, bitter almond oil camphor system Photoepolymerizationinitiater initiater, benzil system Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, thioxanthone system Photoepolymerizationinitiater initiater etc. can be enumerated.
As benzoin ether system Photoepolymerizationinitiater initiater, such as benzoin methyl ether, benzoin ethyl ether, bitter almond oil camphor propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2 can be enumerated, 2-dimethoxy-1,2-diphenylethane-1-ketone, methyl-phenoxide methyl ether etc.
As methyl phenyl ketone system Photoepolymerizationinitiater initiater, such as 2,2-diethoxy acetophenones, 2,2-dimethoxy-2-phenyl acetophenone, 4-phenoxydichloroacetophenone, 4-(tertiary butyl) dichloroacetophenone etc. can be enumerated.
As α-one alcohol system Photoepolymerizationinitiater initiater, such as 2-methyl-2-hydroxypropiophenonepreparation, 1-[4-(2-hydroxyethyl) phenyl]-2-methylpropane-1-ketone can be enumerated, 1-hydroxycyclohexylphenylketone etc.
As aromatic sulfonyl system Photoepolymerizationinitiater initiater, such as 2-naphthalic sulfonic chloride etc. can be enumerated.
As photolytic activity oxime system Photoepolymerizationinitiater initiater, such as 1-phenyl-1,1-propanedione-2-(O-ethoxy carbonyl) oxime etc. can be enumerated.
As bitter almond oil camphor system Photoepolymerizationinitiater initiater, such as bitter almond oil camphor etc. can be enumerated.
As benzil system Photoepolymerizationinitiater initiater, such as benzil etc. can be enumerated.
As benzophenone series Photoepolymerizationinitiater initiater, such as benzophenone, benzoyl phenylformic acid, 3 can be enumerated, 3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone etc.
As thioxanthone system Photoepolymerizationinitiater initiater, such as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone, decyl thioxanthone etc. can be enumerated.
As thermal polymerization, such as 2 can be enumerated, 2 '-azobis isobutyronitrile, 2, the two-2-methylbutyronitrile of 2 '-azo, 2, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo, 4, the two-4-cyanopentanoic acid of 4 '-azo, the two isovaleronitrile of azo, 2, two (2-amidine propane) dihydrochloride of 2 '-azo, 2, two [2-(5-methyl-2-tetrahydroglyoxaline-2-base) propane] dihydrochloride of 2 '-azo, 2, two (the 2-methyl-prop amidine) dithionate of 2 '-azo, 2, two (N, the N '-dimethyleneisobutylamidine) hydrochloride of 2 '-azo, 2, the azo system polymerization starters such as two [N-(2-the carboxy ethyl)-2-methyl-prop amidine] hydrates of 2 '-azo, such as dibenzoyl peroxide, peroxidation toxilic acid tertiary butyl ester, two tertiary hexyl superoxide, tertiary hexyl peroxy-2-ethylhexanoate, tertbutyl peroxide, the peroxidation system polymerization starters such as hydrogen peroxide, such as, Potassium Persulphate, the persulphates such as ammonium persulphate, such as, the combination of persulphate and sodium bisulfite, the reducto oxydative system polymerization starters etc. such as the combination of superoxide and sodium ascorbate.
These polymerization starters also can (only a kind) use separately, in addition, also can two or more combinationally use.
In these polymerization starters, from the advantage etc. that can shorten polymerization time, preferably Photoepolymerizationinitiater initiater can be listed.More preferably benzoin ether system Photoepolymerizationinitiater initiater, α-one alcohol system Photoepolymerizationinitiater initiater can be listed.
When coordinating Photoepolymerizationinitiater initiater as polymerization starter, Photoepolymerizationinitiater initiater such as relative to monomer component 100 mass parts such as with more than 0.01 mass parts, preferably with more than 0.05 mass parts, in addition, such as with below 5 mass parts, preferably coordinate with the ratio below 3 mass parts.
In addition, when coordinating thermal polymerization as polymerization starter, thermal polymerization is not particularly limited, and coordinates with the ratio that can utilize.
Then, in order to prepare monomer composition, as required, make monomer component partially polymerized.
In order to make monomer component partially polymerized, when being combined with Photoepolymerizationinitiater initiater, to the mixture irradiation ultraviolet radiation of monomer component and Photoepolymerizationinitiater initiater.In order to irradiation ultraviolet radiation, the irradiation energy be excited with Photoepolymerizationinitiater initiater carries out irradiating until the viscosity (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) of monomer composition is such as more than 5Pas, be preferably more than 10Pas, in addition, be such as below 30Pas, be preferably below 20Pas.
In addition, when being combined with thermal polymerization, by the mixture of monomer component and thermal polymerization such as more than the decomposition temperature of thermal polymerization, specifically, the viscosity (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) being heated to monomer composition in the same manner as the situation coordinating Photoepolymerizationinitiater initiater under the polymerization temperature of about 20 ~ 100 DEG C is such as more than 5Pas, be preferably more than 10Pas, in addition, be such as below 30Pas, be preferably below 20Pas.
It should be noted that, when making that monomer component is partially polymerized prepares monomer composition, also can first coordinate be selected from (methyl) alkyl acrylate, amide-containing monomer and can copolymerization monomer in monomer component and polymerization starter after, make polymerizing monomer components as described above, coordinate linking agent afterwards.
Linking agent is the polyfunctional compound with multiple ethylenically unsaturated hydrocarbons base, such as hexylene glycol two (methyl) acrylate can be enumerated, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetra methylol propane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, 2 officials such as carbamate (methyl) acrylate can above multifunctional oligopolymer.
Linking agent can be used alone or and uses.
As linking agent, Dipentaerythritol six (methyl) acrylate preferably can be listed.
Linking agent containing proportional be such as more than 0.001 mass parts relative to monomer component 100 mass parts, being preferably more than 0.01 mass parts, in addition, such as, is also below 10 mass parts, is preferably below 1 mass parts.
Thus, monomer composition is prepared.
It should be noted that, with regard to monomer composition, when monomer component generating portion is polymerized, be prepared with the form of the slurry with above-mentioned viscosity.
In the method, then, in the monomer composition of preparation, thermal conductivity particle is coordinated.
That is, in monomer composition, thermal conductivity particle is coordinated in the mode becoming above-mentioned mixing ratio.Thus, preparation contains the heat conductive adhesive raw material of monomer composition and thermal conductivity particle.
It should be noted that, also in monomer composition and/or heat conductive adhesive raw material, the additives such as linking agent, dispersion agent (such as, nonionic surfactant etc.), tackifier, silane coupling agent, softening agent, packing material, antiaging agent, tinting material can be coordinated as required in the proper ratio.
The viscosity (BM viscometer, No.4 rotor, 12rpm, mensuration temperature 23 DEG C) of the heat conductive adhesive raw material obtained is such as below 50Pas, be preferably below 40Pas, being more preferably below 35Pas, is such as more than 5Pas in addition, is preferably more than 10Pas.
Then, the manufacture method of thermal conductivity adhesive sheet 1 is described.
In order to manufacture thermal conductivity adhesive sheet 1, first, the basement membrane 4 shown in the dotted line of set-up dirgram 1, at the face coating heat conductive adhesive raw material implementing lift-off processing of basement membrane 4.
Basement membrane 4 is containing release liner, specifically can list such as polyester film (polyethylene terephthalate film etc.), such as comprise fluorine based polymer (such as tetrafluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene propylene, poly(vinylidene fluoride), tetrafluoraoethylene-hexafluoropropylene copolymer, chlorine vinyl fluoride-vinylidene fluoride copolymer etc.) fluorine mesentery, such as comprise ethylene series resin (polyethylene, polypropylene etc.) ethylene series resin molding, such as polychloroethylene film, polyimide film, polyamide membrane (nylon membrane), plastics systems base material film (synthetic resin film) such as artificial cortina, such as without wood pulp paper, Japan paper, kraft paper, lattice Racine paper, synthetic paper, face is coated with the stationeries such as paper, such as by the complex body etc. of their multiple stratifications.
It should be noted that, when heat conductive adhesive raw material contains Photoepolymerizationinitiater initiater, in order to not hinder ultraviolet to the irradiation of heat conductive adhesive raw material, using the basement membrane 4 of transmitting UV.
As the method being coated with heat conductive adhesive raw material at basement membrane 4, such as roller coat can be enumerated, roller licks formula coating, extrusion coating methods etc. that intaglio plate coating, reversion coating, roller brush, spraying, dipping roller coat, rod paintings, scraper for coating, airblade coating, curtain painting, die lip were coated with, utilized die slot coating machine etc.
As the applied thickness of heat conductive adhesive raw material, such as, be more than 10 μm, be preferably more than 50 μm, be more preferably more than 100 μm, in addition, such as, be also less than 10000 μm, be preferably less than 5000 μm, be more preferably less than 3000 μm.
In the method, then, configuration protection film (not shown) on the film of heat conductive adhesive raw material.In order to configuration protection film on film, configure in the mode that the face implementing lift-off processing of protective membrane is contacted with film.
As protective membrane, such as same with above-mentioned basement membrane 4 film can be enumerated.In addition, when heat conductive adhesive raw material contains Photoepolymerizationinitiater initiater, in order to not hinder ultraviolet to the irradiation of heat conductive adhesive raw material, use the protective membrane of transmitting UV.
In the method, afterwards, the polymerizing monomer components in heat conductive adhesive raw material is made.
In order to make the polymerizing monomer components in heat conductive adhesive raw material, as mentioned above, when being combined with Photoepolymerizationinitiater initiater, to heat conductive adhesive raw material irradiation ultraviolet radiation, or when being combined with thermal polymerization, by heat conductive adhesive heating raw materials.
Thus, form heat conductive adhesive layer 3 by heat conductive adhesive raw material, the stacked basement membrane 4 at the back side of heat conductive adhesive layer 3, the stacked protective membrane (not shown) on surface.
The thickness of heat conductive adhesive layer 3 is such as more than 10 μm, is preferably more than 50 μm, is more preferably more than 100 μm, in addition, such as, is also less than 10000 μm, is preferably less than 5000 μm, is more preferably less than 3000 μm.
Afterwards, heat conductive adhesive layer 3 is laminated in the back side of metal level 2.
Specifically, first, do not illustrate, by the sur-face peeling of protective membrane from heat conductive adhesive layer 3, afterwards, the surface of heat conductive adhesive layer 3 is fitted in the back side of metal level 2.
Thus, the thermal conductivity adhesive sheet 1 possessing metal level 2 and the heat conductive adhesive layer 3 stacked at its back side is obtained.
Be laminated with basement membrane 4 at the back side of thermal conductivity bonding coat 3, basement membrane 4 is peeled off by from heat conductive adhesive layer 3 when the use of thermal conductivity adhesive sheet 1.
The thickness of the thermal conductivity adhesive sheet 1 obtained is such as more than 15 μm, is preferably more than 50 μm, is more preferably more than 100 μm, in addition, such as, is also less than 10000 μm, is preferably less than 5000 μm, is more preferably less than 3000 μm.
The thermal conductivity of direction, the face PD of thermal conductivity adhesive sheet 1 is such as more than 20W/mK, and be preferably more than 50W/mK, being more preferably more than 100W/mK, in addition, is also below 500W/mK.Thermal conductivity is described in detail in the evaluation of the embodiment below.
If more than the above-mentioned lower limit of thermal conductivity of direction, the face PD of thermal conductivity adhesive sheet 1, then can be suitably used for needing the equipment of high-cooling property (aftermentioned).
The thermal conductivity adhesive sheet 1 obtained like this can use as the radiator element of various equipment.
In addition, the thermal conductivity of this thermal conductivity adhesive sheet 1 and binding property (pressure-sensitive adhesive) excellence, therefore fitted (pressure-sensitive adhesive) uses after various equipment and heat release object.Specifically, the heat conductive adhesive layer 3 of thermal conductivity adhesive sheet 1 fitted (pressure-sensitive adhesive) use after heat release object.
Equipment is the equipment needing high-cooling property, specifically, such as semiconductor device, hard disk, LED matrix (TV, illumination, indicating meter etc.), EL device (OLED display, organic EL illuminating etc.), electrical condenser (condenser etc.), battery (lithium ion battery etc.), power module etc. can be enumerated.
Especially because thermal conductivity adhesive sheet 1 especially can improve the thermal conductivity in direction, face, therefore with frivolous miniaturization, may be used for the equipment of the further high thermal diffusivity of requirement, specifically, such as, possess the mobile phone (so-called smart mobile phone) of the function of PC or PDA (personal digital assistant), such as, possess the pocket pc (so-called tablet PC) etc. of touch display/input part.Further, also thermal conductivity adhesive sheet 1 can be used for such as digital camera, projector etc.
In addition, thermal conductivity adhesive sheet 1 can fit in the heat release components such as the chip (CPU etc.) in aforesaid device.
In addition, when thermal conductivity adhesive sheet 1 is configured at the chip be installed on substrate, first in the mode of the outer shape corresponding to substrate, cut-out processing (sharp processing) is carried out to thermal conductivity adhesive sheet 1, afterwards, thermal conductivity adhesive sheet 1 is fitted in the surface of substrate in the mode comprising (covering) chip.During laminating, thermal conductivity adhesive sheet 1 corresponds to the thickness of chip, follows upper surface and the side of chip.Afterwards, when this substrate is contained in housing, thermal conductivity adhesive sheet 1 is also accommodated in the space in housing.
Then, because this thermal conductivity adhesive sheet 1 possesses metal level 2, therefore processibility and operability excellence.
In addition, thermal conductivity adhesive sheet 1 possesses the heat conductive adhesive layer 3 at the back side being laminated in metal level 2 further, and heat conductive adhesive layer 3 is containing the adhesive composition obtained by making the polymerizing monomer components containing (methyl) alkyl acrylate and thermal conductivity particle.Therefore, if heat conductive adhesive layer 3 is fitted in heat release object, then the heat produced from heat release object is conducted to metal level 2 by heat conductive adhesive layer 3, then, along metal level 2, that is, effectively conducts to direction, face PD.Further, while the heat conduction in above-mentioned metal level 2, in heat conductive adhesive layer 3, from heat release object produce heat also along heat conductive adhesive layer 3, that is, effectively conduct to direction, face PD.
Therefore, the excellent thermal conductivity of direction, the face PD of thermal conductivity adhesive sheet 1.
Further, because monomer component is not in fact containing carboxylic monomer, therefore can prevent from resulting from the generation of the corrosion of carboxyl at the back side of metal level 2.Specifically, in the corrosion test described in detail by embodiment below, do not corrode at the back side of metal level 2.Therefore, good outward appearance can be guaranteed, prevent the reliability of the equipment configured from reducing.
It should be noted that, in the thermal conductivity adhesive sheet 1 shown in Fig. 1, only the back side of metal level 2 is provided with heat conductive adhesive layer 3, but shown in the dotted line of such as Fig. 1 and solid line, also further heat conductive adhesive layer 3 can be set on the surface of metal level 2.
That is, as indicated by the dashed line in figure 1, heat conductive adhesive layer 3 can be arranged at surface and this two sides, the back side of metal level 2.
Owing to also not corroding on the two sides of metal level 2 in this situation, it is hereby ensured good outward appearance, prevent the reliability of the equipment configured from reducing.
Embodiment
Below enumerate embodiment and comparative example is described in further detail to the present invention, but the invention is not restricted to these examples.
Embodiment 1
Prepare using 2-ethylhexyl acrylate 80 weight part as principal constituent, as can vinylformic acid 2-methoxy ethyl ester 11.5 weight part, the mixture that mixes as monomer component as hydroxyethyl acrylamide (HEAA) 1.5 weight part of NVP (NVP) 7 weight part of the monomer of amide-containing and the monomer as amide-containing of monomer of copolymerization.
The trade(brand)name " Irgacure 651 " (2 as Photoepolymerizationinitiater initiater is coordinated in the mixture obtained, 2-dimethoxy-1,2-diphenylethane-1-Tong Qiba Japanese firm system) 0.05 weight part and trade(brand)name " Irgacure 184 " (1-hydroxy-cyclohexyl-phenyl-Tong Qiba Japanese firm system) 0.05 weight part.
Then, to mixture irradiation ultraviolet radiation, carry out being polymerized until viscosity (BH viscometer, No.5 rotor, 10rpm, mensuration temperature 30 DEG C) is about 20Pas, prepare the partial polymer (slurry) of the partially polymerized monomer component of monomer component.
Trade(brand)name " KAYARAD DPHA-40H " (dipentaerythritol acrylate is coordinated in slurry 100 weight part of preparation, chemical drug Inc. of Japan) 2 weight parts are as dispersion agent and mix as linking agent, trade(brand)name " Plysurf A212E " (the first industrial pharmaceutical Inc.) for 0.05 weight part, prepared monomer composition.
In the monomer composition obtained, add trade(brand)name " the HigiliteH-42 " (shape: broken shape as aluminium-hydroxide powder, 1 median size: 1 μm) (Showa electrician Inc.) 150 weight parts are as thermal conductivity particle and add as trade(brand)name " Higilite the H-10 " (shape: broken shape of aluminium-hydroxide powder, 1 median size: 55 μm) (Showa electrician Inc.) 150 weight parts, as thermal conductivity particle, have prepared heat conductive adhesive raw material.
The heat conductive adhesive raw material of preparation is coated the basement membrane (trade(brand)name " diafoil MRF38 " as implementing the release liner of the polyethylene terephthalate of lift-off processing to one side; polyester film Inc. of Mitsubishi Chemical) lift-off processing face on; then; the stacked protective membrane (trade(brand)name " diafoil MRF38 ", polyester film Inc. of Mitsubishi Chemical) as implementing the release liner of the polyethylene terephthalate of lift-off processing to one side of the mode that the film of heat conductive adhesive raw material contacts using lift-off processing face with film.
Then, to heat conductive adhesive raw material ultraviolet, (illumination is about 5mW/cm
2) irradiate 3 minutes from both sides (two release liners).
Thus, make the polymerizing monomer components in heat conductive adhesive raw material, define the thermal conductivity bonding coat of thickness 200 μm.
Afterwards; protective membrane is peeled off from thermal conductivity bonding coat; using the one side laminating of thermal conductivity bonding coat to the aluminium foil (the thermal conductivity 237W/mK in direction, face lives light metal paper tinsel Inc.) of the thickness 50 μm as tinsel, make thermal conductivity adhesive sheet (with reference to Fig. 1) thus.
Embodiment 2
Except the Copper Foil (the thermal conductivity 398W/mK in direction, face) tinsel being changed to thickness 35 μm, process similarly to Example 1, made thermal conductivity adhesive sheet.
Comparative example 1
In embodiment 1, except the use level of slurry being set to 95 weight parts and adding except vinylformic acid (AA) 5 weight part of monomer component, process similarly to Example 1, made thermal conductivity adhesive sheet.
Comparative example 2
Preparing except heat conductive adhesive raw material except not adding thermal conductivity particle, having processed similarly to Example 1, having made thermal conductivity adhesive sheet.
(evaluation)
1. the thermal conductivity in a direction
By using the light AC method of the light AC method thermal diffusivity determinator (LaserPIT series) of Ai Fake science and engineering company (ア Le バ ッ Network science and engineering society), obtain the thermal diffusivity of thermal conductivity adhesive sheet, substituted into following formula, obtained the thermal conductivity in the direction, face of thermal conductivity adhesive sheet thus.
Thermal conductivity=density × specific heat × thermal diffusivity
It should be noted that, obtained the specific heat of thermal conductivity adhesive sheet by DSC (differential scanning calorimeter).Specifically, by using the DSC method of Perkin-Elmer Inc. differential scanning calorimeter DSC-7 to obtain.
2. the corrosion (corrosion test) at the back side of metal level
Thermal conductivity adhesive sheet is preserved 1000 hours in the constant temperature and humidity machine of temperature 85 DEG C, relative humidity 85%.Afterwards, thermal conductivity adhesive sheet is taken out from constant temperature and humidity machine, the etch state in the face (back side) relative with heat conductive adhesive layer of visual confirmation metal level.Specifically, after peeling off thermal conductivity adhesive sheet from metal level, the etch state in the face (back side) contacted with heat conductive adhesive layer in visual confirmation metal level.
[table 1]
It should be noted that, provide foregoing invention with the form of the illustrative embodiment of the present invention, but this only illustrates, must not restrictively make an explanation.Those skilled in the art be it is evident that variation of the present invention is also contained in claims of patent.
Utilizability in industry
Thermal conductivity adhesive sheet can use as the radiator element of various equipment.
Claims (4)
1. a thermal conductivity adhesive sheet, is characterized in that, possesses:
Metal level and
At the heat conductive adhesive layer that at least one surface layer of described metal level is folded,
Described heat conductive adhesive layer contain by make polymerizing monomer components containing (methyl) alkyl acrylate and the adhesive composition that obtains and
Thermal conductivity particle,
Described monomer component is not in fact containing carboxylic monomer.
2. thermal conductivity adhesive sheet according to claim 1, is characterized in that,
The monomer of described monomer component also containing amide-containing.
3. thermal conductivity adhesive sheet according to claim 1, is characterized in that,
The thermal conductivity in the direction orthogonal with thickness direction is more than 20W/mK.
4. thermal conductivity adhesive sheet according to claim 1, is characterized in that,
When preserving 1000 hours under the atmosphere of temperature 85 DEG C, relative humidity 85%, do not corrode in the described one side of described metal level.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-168597 | 2012-07-30 | ||
| JP2012168597A JP2014025028A (en) | 2012-07-30 | 2012-07-30 | Heat-conductive adhesive sheet |
| PCT/JP2013/069219 WO2014021090A1 (en) | 2012-07-30 | 2013-07-12 | Heat-conductive adhesive sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104487531A true CN104487531A (en) | 2015-04-01 |
Family
ID=50027772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380038685.2A Pending CN104487531A (en) | 2012-07-30 | 2013-07-12 | Heat-conductive adhesive sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2014025028A (en) |
| KR (1) | KR20150040253A (en) |
| CN (1) | CN104487531A (en) |
| TW (1) | TW201404586A (en) |
| WO (1) | WO2014021090A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111242A (en) * | 2019-06-21 | 2020-12-22 | 日东电工株式会社 | Adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101828644B1 (en) * | 2014-03-25 | 2018-02-14 | 주식회사 엘지화학 | Adhesive composition for heat radiation adhesive tape and heat radiation adhesive tape |
| WO2015156258A1 (en) * | 2014-04-07 | 2015-10-15 | 日本ゼオン株式会社 | Production method for thermally conductive pressure-sensitive adhesive laminated sheet, thermally conductive pressure-sensitive adhesive laminated sheet, and electronic device |
| JP6623474B2 (en) * | 2016-03-28 | 2019-12-25 | 北川工業株式会社 | Heat conductive member, method for manufacturing heat conductive member, and heat conductive structure |
| KR102539196B1 (en) * | 2016-08-18 | 2023-06-02 | 삼성디스플레이 주식회사 | Flexible display device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW459031B (en) * | 1997-05-16 | 2001-10-11 | Nitto Denko Corp | Peelable heat-conductive and pressure-sensitive adhesive and adhesive sheet containing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0942059B1 (en) * | 1996-11-29 | 2004-10-27 | Nitto Denko Corporation | Thermally conductive pressure-sensitive adhesive and adhesive sheet containing the same |
| CA2273890C (en) * | 1996-12-04 | 2006-03-14 | Nitto Denko Corporation | Thermally conductive pressure-sensitive adhesive, adhesive sheet containing the same, and method for fixing electronic part to heat-radiating member with the same |
| JP3810515B2 (en) * | 1997-05-23 | 2006-08-16 | 日東電工株式会社 | Peelable thermally conductive pressure sensitive adhesive and its adhesive sheets |
| JPH10330692A (en) * | 1997-06-03 | 1998-12-15 | Nitto Denko Corp | Thermoconductive and pressure sensitive adhesive, and adhesive sheets by using the same |
| JP5191080B2 (en) * | 2004-05-14 | 2013-04-24 | 日東電工株式会社 | Pressure-sensitive adhesive sheets for application to metal surfaces and articles having metal surfaces |
| JP2007169416A (en) * | 2005-12-21 | 2007-07-05 | Nippon Zeon Co Ltd | Method for peeling pressure-sensitive adhesive sheet |
| JP5281318B2 (en) * | 2008-05-23 | 2013-09-04 | 日東電工株式会社 | Adhesive composition and adhesive sheet for metal surface sticking |
| JP5587220B2 (en) * | 2010-01-29 | 2014-09-10 | 日東電工株式会社 | Thermally conductive adhesive sheet |
-
2012
- 2012-07-30 JP JP2012168597A patent/JP2014025028A/en active Pending
-
2013
- 2013-07-12 KR KR20147035723A patent/KR20150040253A/en not_active Application Discontinuation
- 2013-07-12 WO PCT/JP2013/069219 patent/WO2014021090A1/en active Application Filing
- 2013-07-12 CN CN201380038685.2A patent/CN104487531A/en active Pending
- 2013-07-29 TW TW102127163A patent/TW201404586A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW459031B (en) * | 1997-05-16 | 2001-10-11 | Nitto Denko Corp | Peelable heat-conductive and pressure-sensitive adhesive and adhesive sheet containing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111242A (en) * | 2019-06-21 | 2020-12-22 | 日东电工株式会社 | Adhesive sheet |
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| Publication number | Publication date |
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| KR20150040253A (en) | 2015-04-14 |
| TW201404586A (en) | 2014-02-01 |
| WO2014021090A1 (en) | 2014-02-06 |
| JP2014025028A (en) | 2014-02-06 |
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