CN104212368B - Thermal conductivity bonding sheet - Google Patents

Abstract

The present invention provides a kind of with excellent anti-flammability and thermal conductivity and adhesiveness also excellent thin bonding sheet.Thermal conductivity bonding sheet of the invention has adhesive phase, and the adhesive phase with a thickness of 50 μm or less, in described adhesive layer, 10 μm of D50 average grain diameter or more of particle group A and D50 average grain diameter is cooperated less than 10 μm of particle group B as thermal conductivity particle with the ratio that the ratio between the particle group A and particle group B (weight ratio) are 2:8~8:2.The content of thermal conductivity particle in described adhesive layer is preferably 25 volume % or more and 75 volume % or less.In addition, the thermal conductivity bonding sheet is in the flame retardant test of UL94 standard preferably with the anti-flammability of VTM-0 or V-0.

Description

Thermal conductivity bonding sheet

Technical field

The present invention relates to thermal conductivity bonding sheets.More specifically it is related to the small thermal conductivity bonding sheet of the thickness of adhesive phase.

Background technique

In recent years, mobile device, household electrical appliances etc. gradually minimize, the bonding that its internal member of formation is used when fixed etc. Piece also requires further to be thinned.Due to there is the hot and on fire worry accumulated inside equipment, these bonding sheets are wanted It asks with excellent anti-flammability (nonflammable property).

In the past, as the bonding sheet with anti-flammability, it is known that the bonding sheet (patent document of the fire retardant containing halogen system 1), the bonding sheet (patent document 2~4) of the fire retardant containing phosphate.But the fire retardant of halogen system is in environmental safety side Face there are problem, the fire retardant of phosphate there are when electric/electronic device be in contact failure the problems such as.Therefore, it is grinding Study carefully using the fire retardant other than halogen system, phosphate.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2002-173657 bulletin

Patent document 2: Japanese Unexamined Patent Publication 11-1669 bulletin

Patent document 3: Japanese Unexamined Patent Publication 11-323268 bulletin

Patent document 4: Japanese Unexamined Patent Publication 11-189753 bulletin

Summary of the invention

Problems to be solved by the invention

Sufficient anti-flammability is obtained in order to use the fire retardant other than halogen system, phosphate, is needed within the adhesive layer Increase the use level of fire retardant.But if increasing the use level of fire retardant, generating thickness sometimes can not uniform, adhesive phase The problems such as surface is roughening, adhesiveness reduces.That is, current situation is, fire retardant, the tool other than halogen system, phosphate are used Have excellent anti-flammability and thermal conductivity and adhesiveness also excellent thin adhesive also belongs to unknown.

Therefore, it is also excellent with excellent anti-flammability and thermal conductivity and adhesiveness that the purpose of the present invention is to provide a kind of Adhesive phase the small bonding sheet of thickness.

The means used to solve the problem

The present inventor has carried out research extensively and profoundly in order to achieve the above objectives, as a result, it has been found that containing within the adhesive layer When having 2 kinds of particles with specific average grain diameter as thermal conductivity particle, even if thin adhesive phase, anti-flammability, thermally conductive can be obtained Property and the still excellent bonding sheet of adhesiveness, and complete the present invention.

I.e. the present invention provides a kind of thermal conductivity bonding sheet, with adhesive phase, and the adhesive phase with a thickness of 50 μ M is hereinafter, in described adhesive layer, 10 μm of D50 average grain diameter or more of particle of particle group A and the D50 average grain diameter less than 10 μm Group B is cooperated as thermal conductivity particle with the ratio that the ratio between the particle group A and particle group B (weight ratio) are 2:8~8:2.

The content of thermal conductivity particle in described adhesive layer is preferably 25 volume % or more and 75 volume % or less.

The thermal conductivity bonding sheet is in the flame retardant test of UL94 standard preferably with the anti-flammability of VTM-0 or V-0.

The thermal conductivity of the thermal conductivity bonding sheet is preferably 0.3W/mK or more.

The retentivity (80 DEG C, 300gf) of the thermal conductivity bonding sheet is preferably 2mm or less.

Described adhesive layer is preferably active energy ray curable adhesive phase.

Invention effect

Thermal conductivity bonding sheet of the invention have above-mentioned composition, even if therefore adhesive phase it is thin, thermal conductivity and anti-flammability It is excellent, and adhesiveness is also excellent.

Detailed description of the invention

Fig. 1 is the schematic diagram for indicating thermal characteristics evaluating apparatus.

Specific embodiment

Thermal conductivity bonding sheet of the invention has adhesive phase (adhesive phase is known as " adhesive phase X " sometimes), and And the adhesive phase with a thickness of 50 μm hereinafter, in described adhesive layer, 10 μm of D50 average grain diameter or more of particle group A and D50 Average grain diameter less than 10 μm of particle group B as thermal conductivity particle with the ratio between the particle group A and particle group B (weight ratio) be 2: The ratio of 8~8:2 is cooperated.

Thermal conductivity bonding sheet of the invention can be viscous in the single side with substrate of the single side of substrate with adhesive phase Close piece, the two-sided double-sided adhesive sheet with substrate with adhesive phase of substrate, without substrate without substrate bonding sheet Any one in (no substrate double-sided adhesive sheet).Wherein, from the viewpoint of it can select the various materials to be fixed, Preferably double-sided adhesive sheet, especially from the thickness thinning aspect that can make bonding sheet, preferably without substrate both-sided adhesive Piece.Adhesive phase can may be multilayer for single layer.It should be noted that above-mentioned " substrate " is not included in thermal conductivity bonding sheet Use when the release liner (partition) removed.In addition, in the case where the double-sided adhesive sheet with substrate, as long as at least one is viscous Mixture layer is the specific adhesive phase X.

In this specification, " bonding sheet " also includes " adhesive tape ".In addition, adhesive phase will be formed sometimes in this specification When the composition (coating liquid etc.) that uses be known as " adhesive composition ".

[adhesive phase]

The adhesive phase of the thermal conductivity bonding sheet can play cementability.Such adhesive phase is by adhesive composition It is formed.Such as aftermentioned acrylic adhesive layer is formed by acrylic adhesive composition.

It as the adhesive for constituting above-mentioned adhesive phase, is not particularly limited, but it is viscous to enumerate such as carbamate system Mixture, acrylic adhesive, elastomeric adhesive, silicone-based adhesive, Polyester adhesive, polyamide-based adhesive, ring Oxygen system adhesive, vinyl alkyl ethers system adhesive, fluorine system adhesive etc..Wherein, from weatherability, heat resistance, function, according at This or using the adhesive design easness of purpose from the perspective of, preferred acrylic adhesive.That is, thermal conductivity of the invention Bonding sheet preferably has acrylic adhesive layer.

Above-mentioned acrylic adhesive layer contains acrylic acid series polymeric compounds as basic polymer.Above-mentioned acrylic polymeric Object is containing acrylic monomer (with the monomer of (methyl) acryloyl group in molecule) as the polymer for constituting monomer component. Above-mentioned acrylic acid series polymeric compounds are preferably to contain (methyl) alkyl acrylate as the polymer for constituting monomer component.It needs Bright, acrylic acid series polymeric compounds can be used alone or two or more is applied in combination.

As above-mentioned (methyl) alkyl acrylate, be not particularly limited, but can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) third Olefin(e) acid isopentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid 2- Ethylhexyl, (methyl) Isooctyl acrylate monomer, (methyl) nonyl acrylate, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid Last of the ten Heavenly stems ester, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) Tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid ten Six Arrcostabs, (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid nonadecyl It is (methyl) alkyl acrylate of 1~20 alkyl that ester, (methyl) acrylic acid eicosane base ester etc., which have carbon atom number,.Its In, from the viewpoint of the easy balance for obtaining adhesion characteristic, it is however preferred to have carbon atom number is 1~12 (especially 2~12) Alkyl (methyl) alkyl acrylate, more preferably with carbon atom number be 4~9 alkyl (methyl) acrylic acid alkyl Ester.Above-mentioned (methyl) alkyl acrylate may be used singly or in combin two or more.

Above-mentioned (methyl) alkyl acrylate is relative to the whole monomer components (100 for constituting above-mentioned acrylic acid series polymeric compounds Weight %) ratio be not particularly limited, but preferably 60 weight % or more (such as 60~99 weight %), more preferably 70 Weight % or more (such as 70~98 weight %), further preferably 80 weight % or more (such as 80~98 weight %).

Above-mentioned acrylic acid series polymeric compounds, which can be, only contains above-mentioned (methyl) alkyl acrylate as constituting its monomer The polymer of ingredient, but from can assign function as needed in terms of, more suitably control adhesive various characteristics or Structure of acrylic acid series polymeric compounds etc. is set out, and is also possible to contain above-mentioned (methyl) alkyl acrylate and copolymerizable simultaneously Polymer of the monomer as the monomer component for constituting it.It should be noted that co-polymerized monomer can be used alone or combine Using two or more.

As above-mentioned co-polymerized monomer, monomer containing polar group can be enumerated.As above-mentioned monomer containing polar group, there is no especially It limits, but such as can enumerate: carboxyl group-containing monomer, hydroxyl monomer, nitrogen containing monomer, monomer containing sulfonic group, phosphorous acid-based monomers. It should be noted that monomer containing polar group may be used singly or in combin it is two or more.

Above-mentioned carboxyl group-containing monomer is the monomer in 1 molecule with 1 or more carboxyl, can be the form of acid anhydrides.As upper State carboxyl group-containing monomer, be not particularly limited, but can for example enumerate: (methyl) acrylic acid, itaconic acid, maleic acid, fumaric acid, bar Beans acid, iso-crotonic acid, maleic anhydride, itaconic anhydride etc..It should be noted that carboxyl group-containing monomer can be used alone or combine Using two or more.

Particularly, above-mentioned acrylic acid series polymeric compounds preferably contain substantially no carboxyl group-containing monomer as constitute its monomer at Point.In addition, " containing substantially no " carboxyl group-containing monomer refers to, constitutes in the monomer component of acrylic acid series polymeric compounds and be entirely free of Carboxyl group-containing monomer or carboxyl group-containing monomer are relative to the whole monomer components (100 weight %) for constituting acrylic acid series polymeric compounds Ratio is 0.1 weight % or less.

In the case where above-mentioned acrylic adhesive layer contains aftermentioned thermal conductivity particle, if above-mentioned acrylic polymeric Object contains carboxyl group-containing monomer as its monomer component is constituted, then is difficult to obtain because of thermal conductivity particle sometimes containing containing polarity The effect that cementability caused by base monomer improves, in addition, forming composition, that is, acrylic acid series of acrylic adhesive layer sometimes The mobility of adhesive composition reduces and is difficult to form adhesive phase.Although they the reason of are not also very clear, push away Survey its reason to be: the carboxyl of carboxyl group-containing monomer is reacted with functional group possessed by thermal conductivity particle (such as hydroxyl etc.), makes third Olefin(e) acid system adhesive composition is harder than needed for or keeps adhesive phase harder than required, the wetability reduction of adhesive phase.

If containing hydroxyl monomer as co-polymerized monomer, the dispersibility of thermal conductivity particle becomes well, in addition, propylene Acid system adhesive phase is easy to get the good wettability to adherend.It as above-mentioned hydroxyl monomer, such as can enumerate: (methyl) Acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) propylene Sour 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, methacrylic acid (4- Hydroxymethyl-cyclo-hexyl) methyl esters etc.. Wherein, preferably (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxyl Butyl ester.It should be noted that hydroxyl monomer may be used singly or in combin it is two or more.

If containing nitrogen containing monomer as co-polymerized monomer, appropriate polarity is assigned, acrylic adhesive layer is easy The good adhesion properties such as cementability, bonding reliability to the initial stage of stickup.It as above-mentioned nitrogen containing monomer, such as can enumerate: N- (2- hydroxyethyl) (methyl) acrylamide, N- (2- hydroxypropyl) (methyl) acrylamide, N- (1- hydroxypropyl) (methyl) acrylamide, N- (3- hydroxypropyl) (methyl) acrylamide, N- (2- hydroxybutyl) (methyl) acrylamide, N- hydroxy alkyl (the first such as N- (3- hydroxybutyl) (methyl) acrylamide, N- (4- hydroxybutyl) (methyl) acrylamide Base) acrylamide；N- (methyl) acryloyl morpholine, N- acryloyl group pyrrolidines etc. ring-types (methyl) acrylamide；(first Base) acrylamide, N- replace non-annularities (methyl) acrylamide such as (methyl) acrylamide.Replace (methyl) as above-mentioned N- Acrylamide can be enumerated: the N- alkyl (methyl) such as N- ethyl (methyl) acrylamide, N- normal-butyl (methyl) acrylamide Acrylamide；N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dipropyl (first Base) acrylamide, N, N- diisopropyl (methyl) acrylamide, N, N- bis- (normal-butyl) (methyl) acrylamide, N, N- bis- The N such as (tert-butyl) (methyl) acrylamide, N- dialkyl group (methyl) acrylamide etc..

Further, it as above-mentioned nitrogen containing monomer, such as can enumerate: n-vinyl-2-pyrrolidone (NVP), N- second Alkenyl -2- piperidones, N- vinyl -3- morpholone, N- vinyl -2- caprolactam, N- vinyl -1,3- The N- vinyl cyclic amides such as oxazines -2- ketone, N- vinyl -3,5- morpholine diketone；(methyl) acrylate, (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have the list of amino Body；N- N-cyclohexylmaleimide, N-phenylmaleimide etc. have the monomer of maleimide skeleton；N- methyl clothing Health acid imide, N- ethyl clothing health acid imide, N- butyl clothing health acid imide, N-2- ethylhexyl clothing health acid imide, N- laurel Clothing health imide series monomers such as base clothing health acid imide, N- cyclohexyl clothing health acid imide etc..It should be noted that nitrogen containing monomer can It is two or more to be used singly or in combination.

Wherein, as above-mentioned nitrogen containing monomer, preferably N- hydroxy alkyl (methyl) acrylamide, N- vinyl cyclic acyl Amine, ring-type (methyl) acrylamide, N- replace (methyl) acrylamide, more preferable N- (2- hydroxyethyl) (methyl) propylene Amide, n-vinyl-2-pyrrolidone, N- (methyl) acryloyl morpholine, N, N- diethyl (methyl) acrylamide.

Ratio of the above-mentioned nitrogen containing monomer relative to the whole monomer components (100 weight %) for constituting above-mentioned acrylic acid series polymeric compounds Example is not particularly limited, but its lower limit is preferably 1 weight % or more, more preferably 2 weight % or more.In addition, its upper limit is excellent 10 weight % are selected as hereinafter, more preferably 7 weight % or less.

It as above-mentioned monomer containing sulfonic group, such as can enumerate: styrene sulfonic acid, allyl sulphonic acid, 2- (methyl) acryloyl Amine -2- methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester, (methyl) acryloyl group oxygroup Naphthalene sulfonic acids etc..It should be noted that monomer containing sulfonic group may be used singly or in combin it is two or more.

As above-mentioned phosphorous acid-based monomers, such as 2- hydroxyethyl acryloyl phosphate can be enumerated etc..It needs to illustrate It is that phosphorous acid-based monomers may be used singly or in combin two or more.

The mixing ratio for constituting the above-mentioned monomer containing polar group in the monomer component of above-mentioned acrylic acid series polymeric compounds is not special It does not limit, but is preferably for example 0.1 weight relative to the monomer component total amount (100 weight %) for constituting above-mentioned acrylic acid series polymeric compounds Measure % or more, more preferably 0.5 weight % or more, further preferably 1 weight % or more, further preferably 2 weight % with Upper, further preferably 3 weight % or more, particularly preferably 5 weight % or more.In addition, the cooperation of the above-mentioned monomer containing polar group Ratio is not particularly limited, but for example relative to monomer component total amount (100 weights for constituting above-mentioned acrylic acid series polymeric compounds Amount %) it is preferably 40 weight % or less, more preferably 30 weight % or less, further preferably 25 weight % or less, especially excellent It is selected as 20 weight % or less.The mixing ratio of the above-mentioned monomer containing polar group in above-mentioned monomer component is not particularly limited, but example It is preferably such as 0.1~40 weight % relative to the monomer component total amount (100 weight %) for constituting above-mentioned acrylic acid series polymeric compounds.If Above-mentioned mixing ratio is in above-mentioned range, then the cohesiveness of adhesive phase becomes appropriateness, and high retentivity and bonding can be obtained Power.

In addition, the monomer with alkoxy can be enumerated as above-mentioned co-polymerized monomer.If containing the monomer with alkoxy As co-polymerized monomer, then the wetability of acrylic adhesive layer can be improved, can effectively conduct from adherend (heat Generating source) heat.As the above-mentioned monomer with alkoxy, such as can enumerate: (methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) acrylic methoxy glycol ester, (methyl) methoxyethyl poly- the third two Alcohol ester etc..It should be noted that it is two or more that there is the monomer of alkoxy may be used singly or in combin.

The above-mentioned monomer with alkoxy is relative to whole monomer components (100 weights for constituting above-mentioned acrylic acid series polymeric compounds Amount %) ratio be not particularly limited, lower limit is preferably 3 weight %, more preferably 5 weight %.In addition, its upper limit is preferred For 20 weight %, more preferably 15 weight %.

Further, as above-mentioned co-polymerized monomer, polyfunctional monomer can be enumerated.Pass through above-mentioned polyfunctional monomer, Ke Yi Introducing crosslinked structure in acrylic acid series polymeric compounds, the cohesiveness of adjustable adhesive phase.As above-mentioned polyfunctional monomer, such as It can enumerate: hexylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylic acid Ester, (poly-) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylic acid Ester, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) third Olefin(e) acid ester, tetramethylol methane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, two Vinyl benzene, epoxy acrylate, polyester acrylate, urethane acrylate etc..It should be noted that above-mentioned more officials Energy monomer may be used singly or in combin two or more.

Above-mentioned polyfunctional monomer is relative to the whole monomer components (100 weight %) for constituting above-mentioned acrylic acid series polymeric compounds Ratio is not particularly limited, but its lower limit is preferably 0.01 weight %, more preferably 0.02 weight %.In addition, its upper limit is excellent It is selected as 2 weight %, more preferably 1 weight %.If the ratio of polyfunctional monomer is 0.01 weight % or more, high cohesion is obtained Power is easy to get high retentivity, thus preferably.On the other hand, if the ratio of polyfunctional monomer be 2 weight % hereinafter, if can To inhibit the generation of cohesiveness is excessively high, cementability reduces unfavorable condition, therefore it is preferred that.

In addition, can also enumerate as above-mentioned co-polymerized monomer: (methyl) glycidyl acrylate, allyl glycidyl are sweet Oleyl ether etc. has the monomer of epoxy group；Acrylonitrile, methacrylonitrile etc. have the monomer of cyano；Styrene, Alpha-Methyl benzene second The styrenic monomers such as alkene；The alpha-olefins such as ethylene, propylene, isoprene, butadiene, isobutene；Acrylic acid -2- isocyanic acid Root closes the monomer with isocyanate group such as ethyl ester, methacrylic acid -2- isocyanato ethyl；Vinyl acetate, propionic acid The vinyl esters such as vinyl acetate system monomer；The vinyl ether monomers such as vinyl ethers；(methyl) tetrahydrofurfuryl acrylate etc. has miscellaneous (methyl) acrylate of ring；Fluorine-containing (methyl) acrylate etc. has the monomer of halogen atom；3- methacryloxy third Base trimethoxy silane, vinyltrimethoxysilane etc. have the monomer of alkoxysilyl；Silicone (methyl) acrylic acid Ester etc. has the monomer of siloxanes key；(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid borneol Ester, (methyl) isobornyl acrylate etc. have (methyl) acrylate of alicyclic type hydrocarbon；(methyl) phenyl acrylate, (first Base) benzyl acrylate, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid phenoxy group binaryglycol ester etc. have aromatic series (methyl) acrylate of alkyl etc..

The glass transition temperature (Tg) of above-mentioned acrylic acid series polymeric compounds is not particularly limited, but from being easy to get low bullet The aspect of the acrylic adhesive layer of property, the aspect for being easy to get the good acrylic adhesive layer of difference in height absorbability go out Hair, preferably -10 DEG C of the upper limit, more preferably -20 DEG C, and its lower limit is preferably -70 DEG C, more preferably -65 DEG C.Third The Tg of olefin(e) acid based polymer can be made up of the composition of its monomer component, use level selection to be adjusted.Here, propylene The Tg of sour based polymer refers to, the Tg of the homopolymer based on each monomer for constituting monomer component and the weight percent of the monomer The value that (copolymerization composition) is found out by Fox formula.The value of the Tg of homopolymer can by various known data (Nikkan Kogyo Shimbun " adhering technique handbook (adhering technical Ha Application De Block ッ Network) " etc.) it obtains.

Above-mentioned acrylic acid series polymeric compounds can be obtained by making above-mentioned polymerizing monomer components.As polymerization, not It is particularly limited to, but such as can enumerate polymerisation in solution, emulsion polymerization, bulk polymerization, photopolymerization (active energy beam polymerization). Wherein, preferably by heat, active energy beam (such as alpha ray, β ray, gamma-rays, neutron ray, electron beam etc. ionization property put Ray or ultraviolet light etc.) polymerization, more preferably used the polymerization initiators such as thermal polymerization, Photoepolymerizationinitiater initiater Utilize heat, the polymerization of active energy beam.It should be noted that polymerization initiator may be used singly or in combin It is two or more.

Particularly as above-mentioned polymerization, led from the viewpoint that can shorten polymerization time and even if containing in production The electrical conductivity particle is also uniformly dispersing in the case where the thin adhesive phase of hot particle, can easily produce thickness , it is preferable to use Photoepolymerizationinitiater initiater utilizes active energy beam from the perspective of uniform and smooth surface adhesive phase The polymerization of (especially ultraviolet light).That is, as adhesive phase X, preferably active energy ray curable adhesive phase.? In the case where using solution polymerization process etc., when making thin adhesive phase containing thermal conductivity particle, electrical conductivity grain sometimes Son is difficult to uniformly dispersing, and the surface of adhesive phase becomes coarse.

As above-mentioned Photoepolymerizationinitiater initiater, be not particularly limited, but can for example enumerate: the photopolymerization of benzoin ether system causes Agent, acetophenone system Photoepolymerizationinitiater initiater, α -one alcohol system Photoepolymerizationinitiater initiater, aromatic sulfonyl system Photoepolymerizationinitiater initiater, light are living Property oxime system Photoepolymerizationinitiater initiater, benzoin system Photoepolymerizationinitiater initiater, benzil system Photoepolymerizationinitiater initiater, benzophenone series photopolymerization Initiator, ketal system Photoepolymerizationinitiater initiater, thioxanthones system Photoepolymerizationinitiater initiater etc..It should be noted that Photoepolymerizationinitiater initiater can It is two or more to be used singly or in combination.

As above-mentioned benzoin ether system Photoepolymerizationinitiater initiater, such as can enumerate: benzoin methyl ether, benzoin ethyl ether, Benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- dimethoxy -1,2- diphenylethane - 1- ketone, anisole methyl ether etc..It as above-mentioned acetophenone system Photoepolymerizationinitiater initiater, such as can enumerate: 2,2- diethoxybenzene second Ketone, 2,2- dimethoxy -2- phenyl acetophenone, 1- hydroxycyclohexylphenylketone, 4- phenoxydichloroacetophenone, 4- (tert-butyl) dichloroacetophenone etc..It as above-mentioned α -one alcohol system Photoepolymerizationinitiater initiater, such as can enumerate: 2- methyl -2- hydroxyl Base propiophenone, 1- [4- (2- hydroxyethyl) phenyl] -2- methylpropane -1- ketone etc..As above-mentioned aromatic sulfonyl It is Photoepolymerizationinitiater initiater, such as 2- naphthalene sulfonyl chloride can be enumerated etc..As above-mentioned photolytic activity oxime system Photoepolymerizationinitiater initiater, such as can It enumerates: 1- phenyl -1,1- propanedione -2- (o- ethoxy carbonyl) oxime etc..Cause as the photopolymerization of above-mentioned benzoin system Agent, such as benzoin can be enumerated etc..It as above-mentioned benzil system Photoepolymerizationinitiater initiater, such as can enumerate: benzil etc..As upper Benzophenone series Photoepolymerizationinitiater initiater is stated, such as can be enumerated: benzophenone, benzoyl benzoic acid, 3,3 '-dimethyl -4- Methoxy benzophenone, polyvinyl benzophenone, Alpha-hydroxy cyclohexyl-phenyl ketone etc..Draw as the photopolymerization of above-mentioned ketal system Agent is sent out, such as can be enumerated: dibenzoyl methyl ketal etc..It as above-mentioned thioxanthones system Photoepolymerizationinitiater initiater, such as can enumerate: thioxanthene Ketone, 2-chlorothioxanthone, 2- methyl thioxanthones, 2,4- dimethyl thioxanthone, isopropyl thioxanthone, 2,4- diisopropyl thioxanthene Ketone, decyl thioxanthones etc..

The usage amount of above-mentioned Photoepolymerizationinitiater initiater is not particularly limited, but relative to the above-mentioned acrylic acid series polymeric compounds of composition 100 parts by weight of monomer component, lower limit is preferably 0.01 parts by weight, more preferably 0.05 parts by weight.In addition, its upper limit is preferred For 5 parts by weight, more preferably 3 parts by weight.

In photopolymerization, there is no especially limits for irradiation energy, irradiation time of active energy beam (especially ultraviolet light) etc. It is fixed.The reaction that as long as Photoepolymerizationinitiater initiater activation can be made, monomer component occurs.

As above-mentioned thermal polymerization, 2,2 '-azodiisobutyronitriles, 2,2 '-azo, two -2- methyl fourth can be enumerated Bis- (2 Methylpropionic acid) dimethyl esters of nitrile, 2,2 '-azos, 4,4 '-azo, two -4- cyanopentanoic acid, azobisisovaleronitrile, 2, Bis- [the 2- (5- methyl -2- imidazoline -2- base) third of bis- (2- amidine propane) dihydrochlorides of 2 '-azos, 2,2 '-azos Alkane] dihydrochloride, bis- (the 2- methyl-prop amidine) dithionates of 2,2 '-azos, bis- (N, N '-the dimethylene isobutyls of 2,2 '-azos Base amidine) polymerization of the azos system such as hydrochloride, 2,2 '-azos bis- [N- (2- carboxy ethyl) -2- methyl-prop amidine] hydrates causes Agent；Dibenzoyl peroxide, peroxidating Malaysia tert-butyl acrylate (t- Block チ Le ペ Le マ レ エ ー ト), tert-butyl hydroperoxide, The peroxide such as hydrogen peroxide system polymerization initiator；The persulfates such as potassium peroxydisulfate, ammonium persulfate；Persulfate and bisulfite Redox systems polymerization initiators such as the combination of sodium, the combination of peroxide and sodium ascorbate etc..It should be noted that hot polymerization Conjunction initiator may be used singly or in combin two or more.

The usage amount of thermal polymerization is not particularly limited, such as can be used as polymerization initiator in the past It is selected in the range of.It is molten in the case where being polymerize using heat, such as by monomer component and thermal polymerization Xie Yu solvent appropriate (such as the organic solvents such as toluene, ethyl acetate), such as make it at 20~100 DEG C (preferably 40~80 DEG C) Reaction, it is hereby achieved that acrylic acid series polymeric compounds.

[thermal conductivity particle]

Thermal conductivity bonding sheet of the invention contains thermal conductivity particle within the adhesive layer, therefore can be obtained good thermally conductive Property, and bonding sheet can be made nonflammable, flame can be made to be difficult to spread in bonding sheet.Can be obtained excellent thermal conductivity and Anti-flammability.Thermal conductivity particle can be used alone or two or more is applied in combination.

As above-mentioned thermal conductivity particle, such as metal hydroxides, hydrated metal compound (water and metal compound can be enumerated Object) etc..Range of the kick off temperature of above-mentioned hydrated metal compound at 150~500 DEG C, and be formula M_m1O_n1·XH₂O (here, M is metal, m1, n1 are 1 or more the integer determined by the valence of metal, and X is to indicate the number containing the crystallization water) Compound represented or double salt comprising the compound.

It as above-mentioned metal hydroxides and above-mentioned hydrated metal compound, is not particularly limited, but can for example enumerate: hydrogen Aluminium oxide [Al₂O₃·3H₂O；Or Al (OH)₃], boehmite [Al₂O₃·H₂O；Or AlOOH], magnesium hydroxide [MgOH₂O；Or Mg (OH)₂], calcium hydroxide [CaOH₂O；Or Ca (OH)₂], zinc hydroxide [Zn (OH)₂], silicic acid [H₄SiO₄；Or H₂SiO₃；Or H₂Si₂O₅], iron hydroxide [Fe₂O₃·H₂O or 2FeO (OH)], Kocide SD [Cu (OH)₂], barium hydroxide [BaOH₂O；Or BaO·9H₂O], Zirconium oxide hydrate [ZrOnH₂O], tin oxide hydrate [SnOH₂O], basic magnesium carbonate [3MgCO₃· Mg(OH)₂·3H₂O], hydrotalcite [6MgOAl₂O₃·H₂O], dawsonite [Na₂CO₃·Al₂O₃·nH₂O], borax [Na₂O· B₂O₅·5H₂O], zinc borate [2ZnO3B₂O₅·3.5H₂O] etc..Wherein, from the viewpoint of can be obtained excellent anti-flammability, It is preferred that aluminium hydroxide, magnesium hydroxide.Above-mentioned hydrated metal compound and above-mentioned metal hydroxides can use individually or Two or more is applied in combination in person.

Commercially available product can be used in above-mentioned hydrated metal compound, metal hydroxides.As the commercially available product of aluminium hydroxide, example Trade name " HIGILITE H-31 " (18 μm of average grain diameter) (Showa electrician corporation), trade name " HIGILITE can such as be enumerated H-32 " (8 μm of average grain diameter) (Showa electrician corporation), trade name " HIGILITE H-42 " (1 μm of average grain diameter) (Showa Electrician's corporation), trade name " HIGILITE H-43M " (0.8 μm of average grain diameter) (Showa electrician corporation), trade name " B103ST " (8 μm of average grain diameter) (Japanese light metal corporation) etc..In addition, the commercially available product as magnesium hydroxide, such as can lift Trade name " KISUMA5A " (1 μm of average grain diameter) (consonance chemical industrial company's system), trade name " ECOMAG Z-10 " are (average out 1.4 μm of partial size, Tateho (タ テ ホ) chemical industrial company's system) etc..

Further, it as above-mentioned thermal conductivity particle, such as can enumerate: the gold such as boron nitride, aluminium nitride, silicon nitride, gallium nitride Belong to nitride；Aluminum oxide (aluminium oxide), magnesia, titanium oxide, zinc oxide, tin oxide, copper oxide, nickel oxide, antimony dopant The metal oxides such as the tin oxide of acid.In addition, can also enumerate: silicon carbide, silica, calcium carbonate, barium titanate, potassium titanate, copper, Silver, gold, nickel, aluminium, platinum, carbon black, carbon pipe (carbon nanotube), carbon fiber, diamond etc..

General commercially available product can be used in such thermal conductivity particle.It as the commercially available product of boron nitride, such as can enumerate: commodity Name " HP-40 " (water island alloyed iron corporation), trade name " PT620 " (MOMENTIVE corporation) etc..City as aluminium oxide Product are sold, such as can be enumerated: trade name " AS-50 " (Showa electrician corporation), trade name " AL-13KT " (96 μm of average grain diameter) (Showa electrician corporation) etc..The commercially available product of tin oxide as doping metaantimmonic acid, such as can enumerate: trade name " SN-100S " (stone originates in the manufacture of industry company), trade name " SN-100P " (stone originates in the manufacture of industry company), trade name " SN-100D (water dispersion Product) " (stone originates in the manufacture of industry company) etc..As the commercially available product of titanium oxide, such as can enumerate: (stone originates in trade name " TTO series " The manufacture of industry company) etc..As the commercially available product of zinc oxide, trade name " SnO-310 " (Sumitomo Osaka cement company system can be enumerated Make), trade name " SnO-350 " (manufacture of Sumitomo Osaka cement company), trade name " SnO-410 " (Sumitomo Osaka cement company Manufacture) etc..

Wherein, as above-mentioned thermal conductivity particle, from thermal conductivity, anti-flammability, cost aspect, preferably metal hydroxide Object, hydrated metal compound, metal oxide, more preferably aluminium hydroxide, aluminium oxide, magnesium hydroxide, magnesia.That is, above-mentioned Thermal conductivity particle is preferably selected from least one kind of particle in metal hydroxides, hydrated metal compound and metal oxide, more At least one kind of particle being preferably selected from aluminium hydroxide, aluminium oxide, magnesium hydroxide and magnesia.As above-mentioned thermal conductivity particle, Particularly preferred aluminium hydroxide.

The shape of above-mentioned thermal conductivity particle is not particularly limited, and can be blocky, needle-shaped, plate, stratiform.Bulk includes Such as spherical, rectangular-shape, broken shape or their profiled shape.

Thermal conductivity bonding sheet of the invention in above-mentioned adhesive phase X, 10 μm of D50 average grain diameter or more of particle group A and D50 average grain diameter is less than 10 μm of particle group B as thermal conductivity particle with the ratio between the particle group A and particle group B (weight ratio) Cooperated for the ratio of 2:8~8:2.10 μm of D50 average grain diameter or more of particle group A and D50 average grain diameter is less than 10 μm Particle group B is cooperated at a specific ratio, even if therefore adhesive phase thickness it is thin (even if be 50 μm or less), can also obtain To adhesiveness, excellent and thickness is uniform and the adhesive phase of smooth surface (screening characteristics is excellent).In contrast, it is being used only In the case where 10 μm of D50 average grain diameter or more of particle group A, if the thickness of adhesive phase is thin, it is difficult to obtain thickness together And the adhesive phase of smooth surface (screening characteristics is poor).In addition, in the feelings that particle group B of the D50 average grain diameter less than 10 μm is used only Under condition, if the thickness of adhesive phase is thin, it is difficult to obtain high adhesion.

It should be noted that average grain diameter be found out using the determination of particle size distribution in laser scattering method be with volume The value of benchmark.Specifically, being to measure D50 value by using laser scattering type particle size distribution meter and find out.

The D50 average grain diameter of 10 μm of D50 average grain diameter or more of particle group A is, for example, 10~100 μm, and lower limit is preferably 12 μm, more preferably 15 μm.In addition, its upper limit is preferably 50 μm, more preferably 30 μm, further preferably 25 μm.

The D50 average grain diameter of particle group B of the D50 average grain diameter less than 10 μm is, for example, 0.1 μm more than and less than 10 μm, Lower limit is preferably 0.3 μm, more preferably 0.5 μm.In addition, its upper limit is preferably 8 μm, more preferably 5 μm, further preferably 3 μ m。

The ratio between the particle group A and particle group B (weight ratio) are preferably 3:7~7:3.

The total content of the particle group A and particle group B in above-mentioned adhesive phase X are not particularly limited, but relative to viscous The total volume (100 volume %) of mixture layer X is preferably 25 volume % or more and 75 volume % or less.Its lower limit is more preferably 30 bodies Product %.In addition, its upper limit is more preferably 70 volume %, further preferably 60 volume %.If above-mentioned thermal conductivity particle contains Ratio (total content of particle group A and particle group B) is 25 volume % or more, then readily available good thermal conductivity, good resistance Combustion property, therefore it is preferred that.In addition, if the content ratio (total content of particle group A and particle group B) of above-mentioned thermal conductivity particle is 75 bodies % is accumulated hereinafter, being then able to suppress flexible decline, and be able to suppress the decline of bonding force or retentivity, therefore it is preferred that.It needs It is bright, unit " volume % " used in above-mentioned total content (content ratio) can by using the density of thermal conductivity particle and Conversion is unit " weight % ".

[dispersing agent]

Within the scope of the effect of the invention, steadily divide to make above-mentioned thermal conductivity particle that cohesion not occur It dissipates, dispersing agent can also be contained in above-mentioned adhesive phase X.

It as above-mentioned dispersing agent, is not particularly limited, but for example preferably uses phosphate.As phosphate, there is polyoxy Ethylidene alkyl (or polyoxyethylene base) ether or the phosphate monoester of polyoxyethylene aryl ether, polyoxyethylene ether or The di-phosphate ester of polyoxyethylene aryl ether, phosphotriester, or derivatives thereof etc..Wherein, it is preferable to use polyoxyethylene Alkyl ether or the phosphate monoester of polyoxyethylene aryl ether, di-phosphate ester.Above-mentioned dispersing agent can be used alone or 2 kinds with On be applied in combination.

The content of above-mentioned dispersing agent is not particularly limited, but for example relative to the base polymer in above-mentioned adhesive phase X (for example, above-mentioned acrylic acid series polymeric compounds when as acrylic adhesive layer) 100 parts by weight are preferably 0.01~10 weight Part.Its lower limit is more preferably 0.05 parts by weight, further preferably 0.1 parts by weight.In addition, its upper limit be more preferably 5 parts by weight, Further preferably 3 parts by weight.

General commercially available product, such as trade name " Plysurf (プ ラ イ サ ー Off) can be used in above-mentioned dispersing agent A212E " (the first industrial pharmaceutical corporation), trade name " Plysurf A210G " (the first industrial pharmaceutical corporation), trade name " Plysurf A212C " (the first industrial pharmaceutical corporation), trade name " Plysurf A210F " (first industrial pharmaceutical company System), trade name " Phosphanol (Off ォ ス Off ァ ノ ー Le) RE610 " (Dong Bang chemical company system), trade name " Phosphanol RS710 " (Dong Bang chemical company system), trade name " Phosphanol RS610 " (Dong Bang chemical company system) Deng.

[fluorine system surfactant]

Fluorine system surfactant can also be contained in above-mentioned adhesive phase X.By using above-mentioned fluorine system surfactant, have When base polymer and the adaptation of electrical conductivity particle, frictional resistance reduce, stress dispersibility improves.Therefore, of the invention In thermal conductivity bonding sheet, sometimes available higher adhesiveness.

It as above-mentioned fluorine system surfactant, is not particularly limited, such as there is oxygen C in preferred molecule_2-3Alkylidene and fluorine For the fluorine system surfactant of alkyl.Wherein, from the viewpoint of the dispersibility relative to base polymers such as acrylic acid series polymeric compounds Consider, above-mentioned fluorine system surfactant is preferably to have C in molecule_2-3The non-ionic table of the fluorine system of alkylidene and fluoro alkyl Face activating agent.It should be noted that above-mentioned fluorine system surfactant can be used alone or two or more is applied in combination.

It as above-mentioned fluoro alkyl, is not particularly limited, but for example preferred perfluoroalkyl.Above-mentioned perfluoroalkyl can be 1 Valence may be the multivalence of divalent or more.In addition, above-mentioned fluoro alkyl can also contain double bond, three keys, it can be linear chain structure, Also branched structure, ring structures be can have.The carbon atom number of above-mentioned fluoro alkyl is not particularly limited, but is for example preferably 1 Or 2 or more, more preferably 3~30, further preferably 4~20.It include gas in above-mentioned adhesive phase X when with fluoro alkyl In the case where bubble, the effect for improving bubble Combination and bubble stability can be also obtained.In above-mentioned fluorine system surfactant molecule 1 kind of above-mentioned fluoro alkyl can be imported, two or more can also be imported.

Above-mentioned oxygen C_2-3Alkylidene formula :-R-O- (R is the straight-chain of carbon atom number 2 or 3 or the alkylidene of branched) It indicates.Above-mentioned oxygen C_2-3Alkylidene is not particularly limited, but can for example enumerate: oxygen ethylidene (- CH₂CH₂O-), oxygen propylidene [- CH₂CH(CH₃) O-] etc..Above-mentioned oxygen C_2-3Alkylidene can be to be bonded with alcohol, the end of hydrogen atom on the oxygen atom of end Oxygen atom be bonded with other alkyl ether, end oxygen atom be bonded by carbonyl with other alkyl made of the arbitrary shapes such as ester State.Furthermore it is also possible to have the form of the structure in a part of cyclic structure for ring type ethers, lactone etc..Above-mentioned fluorine system 1 kind of above-mentioned oxygen C can be imported in surfactant molecule_2-3Alkylidene can also import two or more.

Above-mentioned fluorine system surfactant is not particularly limited, but can for example enumerate: will be comprising having oxygen C_2-3The list of alkylidene Copolymer obtained from the polymerizing monomer components of body and the monomer with fluoro alkyl.Above-mentioned fluorine system surfactant is copolymerization It when object, such as can be block copolymer, graft copolymer etc..

As above-mentioned block copolymer, (main chain has oxygen C_2-3The copolymer of alkylidene and fluoro alkyl), do not limit especially It is fixed, but can for example enumerate: polyoxyethylene perfluoroalkyl ethers, polyoxyethylene perfluoroalkyl compound, polyoxypropylene perfluor alkane Base ether, polyoxy isopropylidene perfluoroalkyl ethers, polyoxy ethylene sorbitol alcohol acid anhydride perfluoroalkyl compound, polyoxyethylene polyoxy are sub- Propyl block copolymer perfluoroalkyl compound, polyoxyethylene glycol perfluoroalkyl compound etc..

As above-mentioned graft copolymer, (side chain has oxygen C_2-3The copolymer of alkylidene and fluoro alkyl), do not limit especially It is fixed, such as can enumerate: it at least will be comprising the vinyl compound with polyoxy alkylidene and the vinyl with fluoro alkyl Copolymer obtained from the polymerizing monomer components of based compound, particularly preferred acrylic acid series copolymer.There is polyoxy as above-mentioned The vinyl compound of alkylidene, such as can enumerate: polyoxyethylene (methyl) acrylate, polyoxypropylene (methyl) third Polyoxy alkylidenes (methyl) acrylate such as olefin(e) acid ester, polyoxyethylene polyoxypropylene (methyl) acrylate.As above-mentioned Vinyl compound with fluoro alkyl, such as can enumerate: (methyl) perfluoroethyl butyl ester, (methyl) perfluoroethyl (methyl) acrylic acid containing fluorohydrocarbon such as (methyl) perfluoroalkyl acrylates such as isobutyl ester, (methyl) perfluoroethyl pentyl ester Ester.

Above-mentioned fluorine system surfactant deoxygenation C_2-3Other than alkylidene and fluoro alkyl, it can also not hinder in acrylic acid In the range of dispersibility in based polymer, there is alicyclic type hydrocarbon, aromatic hydrocarbyl, carboxyl, sulfonic group, cyanogen in the molecule The various functional groups such as base, amide groups, amino.For example, when above-mentioned fluorine system surfactant is vinyl based copolymer, as monomer Ingredient, can be used can be with the vinyl compound with polyoxy alkylidene and the vinyl compound with fluoro alkyl The monomer component of copolymerization.Such monomer that can be copolymerized can be used alone or two or more is applied in combination.

As the above-mentioned monomer component that can be copolymerized, for example, being suitable for using (methyl) acrylic acid hendecane base ester, (methyl) third (methyl) acrylic acid such as olefin(e) acid dodecyl ester C_1-20Arrcostab；(methyl) acrylic acid ring pentyl ester etc. has alicyclic type hydrocarbon (methyl) acrylate；(methyl) phenyl acrylate etc. has (methyl) acrylate of aromatic hydrocarbyl.In addition, can also lift Out: the carboxyl group-containing monomers such as maleic acid, crotonic acid；The monomers containing sulfonic group such as sodium vinyl sulfonate；The virtues such as styrene, vinyltoluene Fragrant race's vinyl compound；The alkene such as ethylene, butadiene or dienes；The vinyl ethers such as vinyl alkyl ethers；Acrylamide Equal amide-containings monomer；The emulsion stabilities such as (methyl) acryloyl morpholine；(methyl) acrylic acid methylglycidyl esters etc. contain Glycidyl monomer；The monomers containing isocyanate group such as 2- methacryloxyethyl isocyanates；Dipentaerythritol six Multi-functional co-polymerized monomer such as (methyl) acrylate, divinylbenzene (polyfunctional monomer) etc..

The weight average molecular weight of above-mentioned fluorine system surfactant is not particularly limited, but for example less than 20000 (for example, 500 Above and less than 20000) when, reduce close between the base polymers such as above-mentioned acrylic acid series polymeric compounds and above-mentioned thermal conductivity particle Conjunction property, the effect of frictional resistance are high.In addition, and with 20000 or more weight average molecular weight (such as 20000~100000, preferably 22000~80000, when the fluorine system surfactant of more preferable 24000~60000), contain bladdery feelings in above-mentioned adhesive phase Under condition, the Combination of bubble, the stability for the bubble being mixed with are got higher.

It as the usage amount (solid component) of fluorine system surfactant, is not particularly limited, but for example relative to for shape At 100 parts by weight of whole monomer components (100 parts by weight of base polymer) of the base polymers such as above-mentioned acrylic acid series polymeric compounds, Preferably 0.01~5 parts by weight.Its lower limit is preferably 0.02 parts by weight, further preferably 0.03 parts by weight.In addition, its upper limit Preferably 3 parts by weight, further preferably 2 parts by weight.If above-mentioned usage amount is 0.01 parts by weight or more, in above-mentioned adhesive Containing in the case where bubble the stability of bubble can be obtained, if 5 parts by weight hereinafter, good bond properties then can be obtained in layer.

The case where from than above-mentioned dispersing agent, above-mentioned fluorine system surfactant is used alone less content, make above-mentioned gold Belong to hydroxide and/or above-mentioned hydrated metal compound does not occur cohesion and steadily exists to which the stress of adhesive phase disperses Property improve and from the perspective of capable of expecting higher adhesiveness, above-mentioned dispersing agent and upper can be used together in above-mentioned adhesive phase X State fluorine system surfactant.And with above-mentioned dispersing agent and in the case where above-mentioned fluorine system surfactant, mixing ratio does not have Be particularly limited to, but the ratio between above-mentioned dispersing agent and above-mentioned fluorine system surfactant (weight ratio) be preferably 1:20~20:0.01, it is more excellent It is selected as 1:10~10:0.01, further preferably 1:5~5:0.01.

As with oxygen C_2-3The fluorine system surfactant of alkylidene and fluoro alkyl and weight average molecular weight less than 20000 Concrete example, trade name " フ タ ー ジ ェ Application ト 251 " (Co., Ltd.'s Neos system), trade name " FTX-218 " (strain formula can be enumerated Commercial firm's Neos system), trade name " Megafac (メ ガ Off ァ ッ Network) F-477 " (DIC corporation), trade name " Megafac F- 470 " (DIC corporations), trade name " Surflon (サ ー Off ロ Application) S-381 " (AGCSeimichemical corporation), quotient The name of an article " Surflon S-383 " (AGC Seimichemical corporation), trade name " Surflon S-393 " (AGC Seimichemical corporation), trade name " Surflon KH-20 " (AGC Seimichemical corporation), trade name " Surflon KH-40 " (AGC Seimichemical corporation) etc..As with oxygen C_2-3Alkylidene and fluoro alkyl, simultaneously And weight average molecular weight be 20000 or more fluorine system surfactant concrete example, trade name " Eftop (エ Off ト ッ プ) can be enumerated EF-352 " (Mitsubishi Materials electronics is melted into corporation), trade name " Eftop EF-801 " (Mitsubishi Materials electronics be melted into corporation), trade name " Unidyne (ユ ニ ダ イ Application) TG-656 " (Daikin Industries corporation) Deng.

[crosslinking agent]

From the viewpoint of the cohesiveness that can adjust adhesive phase, crosslinking agent can also be contained in above-mentioned adhesive phase X. Known usual crosslinking agent can be used in above-mentioned crosslinking agent, such as can enumerate: epoxy crosslinking agent, isocyanates system crosslinking agent, Silicone-based crosslinking agent, oxazoline system crosslinking agent, aziridine system crosslinking agent, silane system crosslinking agent, alkyl etherified melamine system hand over Join agent, metal complex system crosslinking agent etc..Wherein, preferred isocyanate system crosslinking agent, epoxy crosslinking agent.

It as above-mentioned isocyanates system crosslinking agent, such as can enumerate: toluene di-isocyanate(TDI), hexa-methylene diisocyanate Ester, isophorone diisocyanate, eylylene diisocyanate, hydrogenation eylylene diisocyanate, diphenylmethyl Alkane diisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethyl xylylen diisocyanate, naphthalene diisocyanate Ester, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate and these isocyanates and trimethylolpropane The adduct etc. of equal polyalcohols.Furthermore it is also possible to use the isocyanate group in 1 molecule at least one or more and 1 or more The compound of unsaturated bond, specifically (methyl) acrylic acid 2- isocyanato ethyl etc..

As above-mentioned epoxy crosslinking agent, such as can enumerate: bisphenol-A, the epoxy system resin of epichlorohydrin type, ethylidene shrink Glyceryl ether, polyethylene glycol diglycidyl base ether, diglycidyl ether, glycerol triglycidyl ether, 1,6- oneself Glycol glycidyl ether, trimethylolpropane tris glycidyl ether, diglycidylaniline, diamines glycidyl Amine, N, N, N ', N '-four glycidyl group m-xylene diamine and bis- (N, the N '-diamines glycidyl-amino methyl) rings of 1,3- Hexane etc..

The content of above-mentioned crosslinking agent is not particularly limited, but for example relative to the above-mentioned acrylic acid in above-mentioned adhesive phase X 100 parts by weight of the base polymers such as based polymer, preferably 0.01~5 parts by weight.Its upper limit is more preferably 3 parts by weight, into one Step is preferably 2 parts by weight.Good flexibility can be obtained and making above-mentioned 5 parts by weight of content or less, by for 0.01 weight Part or more so that high coherency can be obtained.

[tackifying resin]

From the viewpoint of further increasing from adhesiveness, tackifying resin can also be contained in above-mentioned adhesive phase X.Especially It is, when not containing carboxyl group-containing monomer in the monomer component for constituting the base polymers such as above-mentioned acrylic acid series polymeric compounds, if bonding The thickness of oxidant layer is thin, then is difficult to obtain high adhesion, therefore preferably comprise tackifying resin.As above-mentioned tackifying resin, without spy It does not limit, but is not easy from when making monomer component copolymerization obtain acrylic acid series polymeric compounds by irradiating ultraviolet light, being used in combination The reasons why causing polymerization to hinder considers the tackifying resin, it is preferable to use hydrogenation type.As the tackifying resin of hydrogenation type, such as can lift Out to rosin series resin, petroleum line resin, terpenic series resin, coumarone indene system resin, phenylethylene resin series, alkyl phenolic tree Derivative obtained from the tackifying resins such as rouge, xylene resin are hydrogenated (hydrogenation type rosin series resin, hydrogenation type petroleum tree Rouge, hydrogenation type terpenic series resin etc.).Wherein, preferred hydrogenation type rosin series resin.It viscosifies and sets as above-mentioned hydrogenation type rosin series Rouge, such as can enumerate forms the unmodified rosins such as gum rosin, wood rosin, Starex (undressed rosin) modification by hydrogenation Modified rosin etc..

The softening point of above-mentioned tackifying resin is not particularly limited, but such as preferably 80~200 DEG C, more preferably 90~ 200℃.By making the softening point of tackifying resin in the range, so that cohesiveness further increases.

The content of above-mentioned tackifying resin is not particularly limited, but poly- relative to the above-mentioned acrylic acid series in above-mentioned adhesive phase Close 100 parts by weight of base polymers, preferably 1~50 parts by weight such as object.Its lower limit is more preferably 2 parts by weight, further preferably For 3 parts by weight.In addition, its upper limit is more preferably 40 parts by weight, further preferably 30 parts by weight.By making above-mentioned content 50 Parts by weight are hereinafter, this makes it possible to obtain high cohesiveness, and by the way that more than for 1 parts by weight, this makes it possible to obtain high bonding forces.

General commercially available product can be used in above-mentioned tackifying resin, and such as trade name " Super ester (ス ー can be used パ ー エ ス テ Le) A-100 " (95~105 DEG C of softening point, Arakawa Chemical Industries corporation), trade name " Super ester The hydrogenations type rosin series resins such as A-125 " (120~130 DEG C of softening point, Arakawa Chemical Industries corporation).

[acrylic oligomers]

From the viewpoint of further increasing from adhesiveness, above-mentioned adhesive phase X can also contain acrylic oligomers.On State acrylic oligomers be glass transition temperature (Tg) is higher compared with above-mentioned acrylic acid series polymeric compounds, weight average molecular weight more Small polymer has and polymerization obstruction is worked and be not susceptible in the polymerization for having used ultraviolet light as tackifying resin The advantages of.

[silane coupling agent]

From further increasing the viewpoint of bonding force, endurance, further increase above-mentioned thermal conductivity particle and above-mentioned acrylic acid From the viewpoint of the compatibility of the base polymers such as based polymer, silane coupling agent can also be contained in above-mentioned adhesive phase X.

It can be suitable for that such as the third oxygen of 3- epoxy can be enumerated using well known silane coupling agent as above-mentioned silane coupling agent Base propyl trimethoxy silicane, 3- epoxy propoxy propyl triethoxysilane, 3- glycidoxypropyl diethoxy Base silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane etc. contain epoxy silane coupling；3- aminopropyl three Methoxy silane, N-2- (amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- triethoxy-silicane Base-N- (1,3- dimethyl butane) propylamine etc. contains amino silicane coupling agent；3- acryloxypropyl trimethoxy silicon Alkane, 3- methacryloxypropyl etc. contain (methyl) acrylic (ア Network リ Le base) silane coupling agent； Coupling agents containing isocyanato silanes such as 3- isocyanatopropyl triethoxysilane etc..Above-mentioned silane coupling agent can be single It solely uses, can also be mixed with two or more.

The content of above-mentioned silane coupling agent is not particularly limited, such as relative to the above-mentioned propylene in above-mentioned adhesive phase X 100 parts by weight of the base polymers such as sour based polymer, preferably 0.01~10 parts by weight.Its lower limit is more preferably 0.02 weight Part, further preferably 0.05 parts by weight.In addition, its upper limit is more preferably 5 parts by weight, further preferably 2 parts by weight.Pass through Above-mentioned silane coupling agent is used in above range, so that cohesiveness, durability further increase.

[bubble]

Above-mentioned adhesive phase X can be the adhesive phase containing bubble.It is above-mentioned can be to viscous containing bladdery adhesive phase Mixture layer assigns thickness and resiliency, and the concave-convex performance on landfill adherend surface, i.e. concave-convex absorbability (concave-convex tracing ability) mention It is high.

[other additives]

Except base polymers, above-mentioned thermal conductivity particle, above-mentioned point such as above-mentioned acrylic acid series polymeric compounds in above-mentioned adhesive phase X Powder, above-mentioned fluorine system surfactant, above-mentioned crosslinking agent, above-mentioned tackifying resin, above-mentioned acrylic oligomers, above-mentioned silane are even Join other than agent, other additives can also be contained depending on the application.As above-mentioned other additives, for example, can enumerate plasticizer, Filler, anti-aging agent, colorant (pigment, dyestuff etc.) etc..

Above-mentioned adhesive phase X with a thickness of 50 μm or less (such as 1~50 μm), as lower limit, preferably 5 μm, further Preferably 10 μm, particularly preferably 20 μm.By make it is above-mentioned with a thickness of 50 μm hereinafter, adhesive phase becomes soft, can be obtained excellent Different resistance to resilience.In addition, after being punched to adhesive phase, being punched position when bonding sheet is processed as various shape It is not susceptible to be bonded (adhesion) again, thus excellent in workability.In addition, the decline of the bonding force caused by making thinner is few, therefore Adhesiveness is excellent.If above-mentioned with a thickness of 1 μm or more, screening characteristics is excellent.For bonding sheet of the invention, due to above-mentioned bonding The thickness of oxidant layer is in above range, therefore the problems such as be not susceptible to thin-walled spot (か The れ) after coating.

Above-mentioned adhesive phase X can by by the base polymers such as above-mentioned acrylic acid series polymeric compounds, above-mentioned thermal conductivity particle and The adhesive composition that above-mentioned dispersing agent being added as needed etc. mixes is formed.Specifically, for example, will be used to form The monomer component of the base polymers such as above-mentioned acrylic acid series polymeric compounds, above-mentioned polymerization initiator (such as Photoepolymerizationinitiater initiater, hot polymerization Close initiator etc.), the mixing such as solvent appropriate (toluene, ethyl acetate etc.), prepare monomer solution, which carried out pair It should prepare in the polymerization reaction of the type of polymerization initiator comprising bases such as acrylic acid series polymeric compounds made of monomer component copolymerization Then the polymer solution of polymer cooperates above-mentioned thermal conductivity particle, above-mentioned dispersion as needed in the polymer solution Agent etc. prepares the adhesive composition with the viscosity for being suitable for coating.In addition, being carried out by ultraviolet light isoreactivity energy-ray When solidification, it is mixed can also will to be used to form monomer component, Photoepolymerizationinitiater initiater of the base polymers such as acrylic acid series polymeric compounds etc. It closes, prepares monomer mixture, the irradiation of ultraviolet light isoreactivity energy-ray is carried out to the monomer mixture, preparation includes only part The composition (slurries) of partial polymer obtained by polymerizing monomer components, then cooperate in the slurries above-mentioned thermal conductivity particle, Above-mentioned dispersing agent as needed etc. is prepared the composition with the viscosity for being suitable for coating, and is formed using the composition Adhesive phase X.

As described above, especially using the method to form adhesive phase is irradiated by active energy beam, Even if it is equal can also easily to produce the electrical conductivity particle when making the thin adhesive phase containing electrical conductivity particle One ground disperses, thickness is uniform and the adhesive phase of smooth surface.

From screening characteristics it is excellent from the viewpoint of, above-mentioned adhesive composition preferably has appropriate viscosity.As above-mentioned viscous The viscosity of mixture composite, such as preferably 0.5~50Pas, lower limit are more preferably 1Pas, further preferably 5Pa s.In addition, the upper limit is more preferably 40Pas.If above-mentioned viscosity be 50Pas hereinafter, if when forming adhesive phase X, adhesive The coating of composition becomes easy.It should be noted that in the present specification, viscosity, which refers to, uses BH viscosimeter as viscosity Meter, in rotor: No.5 rotor, revolving speed: 10rpm, measuring temperature: the viscosity measured under conditions of 30 DEG C.

The viscosity of above-mentioned adhesive composition can for example wait to adjust by the following method, which comprises cooperation The method of the various component of polymer such as acrylic rubber, thickening property additive；The list of acrylic acid series polymeric compounds will be used to form Body ingredient (for example, being used to form monomer components such as (methyl) acrylate of acrylic acid series polymeric compounds etc.) is partially polymerized and is formed The method etc. of partial polymer.

[substrate]

As above-mentioned base material, it is not particularly limited, such as can enumerate: containing polyethylene terephthalate (PET) etc. The acrylic resins such as polyester based resin, polymethyl methacrylate, polycarbonate, triacetyl cellulose, polysulfones, polyarylate, The plastic foil of the materials such as polyimides, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer. Wherein, from the viewpoint of excellent in flame retardance, preferred polyimide film.

The material of above-mentioned plastic foil can be a kind, can also combine two or more.

The thickness of above-mentioned substrate can be selected suitably depending on the application, and for example, 2~250 μm.Its lower limit is preferably 8 μm, more Preferably 10 μm.In addition, its upper limit is preferably 150 μm, more preferably 50 μm, further preferably 30 μm.If above-mentioned with a thickness of 2 μm or more, then available sufficient bonding force and retentivity, anti-flammability.By make it is above-mentioned with a thickness of 250 μm hereinafter, to viscous Mixture layer becomes soft, the excellent bonding sheet of readily available resistance to resilience.It should be noted that above-mentioned substrate can have single layer With any form of multilayer.Furthermore it is possible to be appropriately carried out at such as Corona discharge Treatment, plasma to the surface of above-mentioned substrate Usual surface treatment known in chemical treatments such as the physical treatments such as reason, primary coat processing etc..

In the present invention, from can make bonding sheet overall thickness it is very thin from the viewpoint of, preferably without substrate without substrate Double-sided adhesive sheet.

[adhesive phase other than adhesive phase X]

When thermal conductivity bonding sheet is the double-sided adhesive sheet with substrate, at least single side is above-mentioned adhesive phase X, another Face can be above-mentioned adhesive phase X or other adhesive phases.As other adhesive phases, as long as not damaging of the invention Effect is just not particularly limited, such as can enumerate by carbamate system adhesive, acrylic adhesive, rubber series bonding Agent, silicone-based adhesive, Polyester adhesive, polyamide-based adhesive, epoxy adhesive, the bonding of vinyl alkyl ethers system The known usual adhesive phase that adhesive well known to agent, fluorine system adhesive etc. is formed.

[release liner]

The adhesive layer surface (adhesive surface) of thermal conductivity bonding sheet of the invention can be carried out with release liner protection until Until when use.It should be noted that each adhesive surface can use 2 when thermal conductivity bonding sheet of the invention is double-sided adhesive sheet Partition is protected respectively, also be can use the partition that 1 two sides is release surface and is protected in the form of being wound into a roll tubular. Release liner is used as the protection materials of adhesive phase, is stripped when bonding sheet is pasted on adherend.In addition, peeling liner Pad also works as the supporter of adhesive phase.It should be noted that release liner can also be not provided with.

As above-mentioned release liner, usual peeling paper etc. can use, specifically, for example, except at least one table Face has other than the substrate of the lift-off processing layer formed by stripping treatment agent, can also use by fluorine system polymer (such as poly- four Vinyl fluoride, polychlorotrifluoroethylene, polyvinyl fluoride, Kynoar, tetrafluoraoethylene-hexafluoropropylene copolymer, chlorine vinyl fluoride-are inclined Fluoride copolymers etc.) the low cementability substrate that is formed or by non-polar polymer (such as alkene such as polyethylene, polypropylene It is resin etc.) the low cementability substrate etc. that is formed.

It as above-mentioned release liner, such as can be suitable for being formed with removing using at least one side in release liner substrate The release liner of process layer.As such release liner substrate, polyester film (polyethylene terephthalate film can be enumerated Deng), olefin-based resin film (polyethylene film, polypropylene screen etc.), polychloroethylene film, polyimide film, PA membrane (nylon membrane), The plastics such as artificial cortina system base material film (synthetic resin film), (upper matter paper and paper, brown paper, glassine paper, synthetic paper, face apply stationery Paper etc.), and pass through lamination, coextrusion etc. for substrate made of their multiple stratifications (2~3 layers of complexs) etc..

As the stripping treatment agent for constituting above-mentioned lift-off processing layer, it is not particularly limited, but silicone-based can be used for example Stripping treatment agent, fluorine system stripping treatment agent, chain alkyl system stripping treatment agent etc..Stripping treatment agent can be used alone or combine Use two or more.It should be noted that the thickness of release liner, forming method etc. are not particularly limited.

The manufacturing method of bonding sheet of the invention is different according to composition of above-mentioned adhesive composition etc., does not limit especially It is fixed, it can use well known forming method, for example, the methods of (1) below~(3) can be enumerated.

(1) by monomer component, the monomer component comprising being used to form the base polymers such as above-mentioned acrylic acid series polymeric compounds Partial polymer, 10 μm of D50 average grain diameter or more of particle group B of particle group A, the D50 average grain diameter less than 10 μm, according to need The adhesive composition coating (coating) of the above-mentioned dispersing agent wanted etc. forms composition layer, makes the combination on substrate or partition Nitride layer solidifies (such as heat cure, the solidification that utilizes the irradiation of ultraviolet light isoreactivity energy-ray to carry out), forms adhesive phase and makes The method for making bonding sheet.

(2) base polymers such as above-mentioned acrylic acid series polymeric compounds (including polymer solution etc.), D50 average grain diameter 10 will be made μm or more particle group B of particle group A, the D50 average grain diameter less than 10 μm, above-mentioned dispersing agent as needed etc. it is equably molten Adhesive composition coating (coating) obtained from solution, dispersion is dried on substrate or partition, forms adhesive phase, comes The method for manufacturing bonding sheet.

(3) method that the bonding sheet further progress manufactured in above-mentioned (1) is dry.

As the curing method in above-mentioned (1)~(3), even if lead from the excellent viewpoint of productivity and being formed to contain It is also capable of forming when the thin adhesive phase of hot particle from the viewpoint of thickness is uniform and the adhesive phase of smooth surface, preferably Cured method (carrying out cured method in particular with ultraviolet light) is carried out using active energy beam.It should be noted that Solidify the obstruction by the oxygen in air sometimes using what active energy beam carried out, thus, for example it is preferred that by bonding It is bonded partition in oxidant layer, in a nitrogen atmosphere solidify etc. to block oxygen.

It, can will be by containing thermal conductivity above-mentioned it should be noted that when to obtain containing bladdery adhesive phase The bubbles adhesive composition for importing bubble (gas for forming bubble) in the adhesive composition of particle and being obtained by mixing On face as defined in being coated on, contain bladdery adhesive phase to be formed.

As the method by above-mentioned adhesive composition coating (coating) on defined face, well known coating can be used Method is not particularly limited, but can for example enumerate: roller coating, roller lick coating, intaglio plate coating, reversion coating, roller brush, spraying, dipping Roller coating cloth, blade coating, airblade coating, curtain coating, lip coating, utilizes extrusion coating methods of die coating machine etc. etc. at stick painting.

In order to cope with the miniaturization of mobile device, household electrical appliances in recent years etc., the thickness of thermal conductivity bonding sheet of the invention is (total Thickness) it is for example preferably 5~270 μm.Its lower limit is more preferably 15 μm, further preferably 20 μm.In addition, its upper limit is more preferable It is 200 μm, further preferably 100 μm, particularly preferably 50 μm.It is above-mentioned with a thickness of 5 μm or more by making, to be easy to follow Height difference part, difference in height absorbability improve.By make it is above-mentioned with a thickness of 270 μm hereinafter, to resistance to resilience it is further excellent. It should be noted that the thickness (overall thickness) of thermal conductivity bonding sheet is the thickness from an adhesive surface to another adhesive surface, no Thickness including release liner.

180 ° of peel adhesions (180 ° of peel adhesions) of the above-mentioned adhesive phase X of thermal conductivity bonding sheet of the invention (23 DEG C, 50%RH, tensile speed 300mm/min, 180 ° of peel angle of stripping conditions, to SUS304 steel plate) be preferably 2N/ 20mm or more (such as 2~20N/20mm), more preferably 2.5N/20mm or more (such as 2.5~20N/20mm).Thermal conductivity bonding When piece is double-sided adhesive sheet, 180 ° of peel adhesions of preferably at least one adhesive surface are met the above range.Above-mentioned 180 ° of removings Bonding force can for example be measured by the method recorded in " (2) 180 ° of peel adhesions " of aftermentioned (evaluation).

The thermal conductivity of thermal conductivity bonding sheet of the invention is preferably 0.3W/mK or more.Thermal conductivity for example can be by rear The method recorded in " (3) thermal conductivity " of (evaluation) stated measures.

Thermal conductivity bonding sheet of the invention is in the flame retardant test of UL94 standard preferably with the resistance of VTM-0 or V-0 Combustion property.Above-mentioned anti-flammability can for example be evaluated by the method recorded in " (4) anti-flammability " of aftermentioned (evaluation).

The retentivity (80 DEG C, 300gf) that the face with above-mentioned adhesive phase X of thermal conductivity bonding sheet of the invention measures is preferred For 2mm or less, more preferably 1mm or less, further preferably 0.6mm or less, particularly preferably 0.3mm or less.In addition, this hair The retentivity (80 DEG C, 100gf) of bright thermal conductivity bonding sheet measured with the face of above-mentioned adhesive phase X is preferably 2mm or less, more Preferably 1mm or less, further preferably 0.3mm or less, particularly preferably 0.2mm or less.Thermal conductivity bonding sheet is double-sided adhesive When closing piece, the retentivity of preferably at least one adhesive surface is met the above range.Above-mentioned retentivity (can for example be commented by aftermentioned Valence) " (5) retentivity " in method for recording measure.

For thermal conductivity bonding sheet of the invention, even if adhesive phase is thin, thermal conductivity, anti-flammability and adhesiveness are also excellent It is different, thus can be suitble to mobile device (such as mobile phone, smart phone, portable information terminal etc.), family's electrical article (such as count Code camera, video camera, PC etc.), hard disk, LED illumination, lithium ion battery etc. constitute used in the inside of electronic equipments Component (electronic equipment member of formation) is fixed etc. with using on the way.In recent years, electronics miniaturization densification develops, It becomes difficult to be discharged into device external using the heat that inside generates when electronic equipment, therefore there are electronic equipment internals due to high fever The worry of burning.Thermal conductivity bonding sheet of the invention has excellent thermal conductivity and anti-flammability, therefore is suitable for heat and is easy accumulation It is used in the fixed of electronic equipment member of formation of the electronic equipment internal of internal small-sized or slim (such as 1~20mm of thickness) On the way.

Embodiment

More specific description is carried out to the present invention hereinafter, enumerating embodiment and comparative example.But the present invention is not limited to this.

(embodiment 1)

It is being mixed with 82 parts by weight of 2-EHA, 12 parts by weight of acrylic acid 2- methoxy acrylate, N- ethylene 5 parts by weight of base -2-Pyrrolidone (NVP), 1 parts by weight of hydroxyethyl acrylamide (HEAA) are mixed as the monomer of monomer component In object, cooperate trade name " Irgacure651 " (2,2- dimethoxy -1,2- diphenyl second as Photoepolymerizationinitiater initiater Alkane -1- ketone, the manufacture of BASF JAPAN company) 0.05 parts by weight and trade name " Irgacure184 " (1- hydroxy-cyclohexyl benzene Base ketone, the manufacture of BASF JAPAN company) 0.05 parts by weight, then irradiate ultraviolet light until viscosity (BH viscosimeter No.5 rotor, 30 DEG C of 10rpm, measuring temperature) become about 20Pas, the mixtures of production part polymerizing monomer components be (monomer mixture Partial polymer, slurries).

Dipentaerythritol hexaacrylate (trade name of the addition as polyfunctional monomer in above-mentioned 100 parts by weight of slurries " KAYARAD DPHA-40H ", Japanese chemical drug corporation are made) 0.05 parts by weight and the trade name " PLYSURF as dispersing agent A212E " (manufacture of the first industrial pharmaceutical company) 1 parts by weight.In addition, trade name of the addition as aluminium-hydroxide powder " HIGILITE H-31 " (shape: broken shape, average grain diameter: 18 μm, the manufacture of Showa electrician company) 100 parts by weight and conduct Trade name " HIGILITE the H-42 " (shape: broken shape, average grain diameter: 1 μm, Showa electrician's corporation of aluminium-hydroxide powder Make) 100 parts by weight as thermal conductivity particle, obtain composition.

Release liner (trade name " the DIAFOIL of the polyethylene terephthalate of lift-off processing is implemented in single side The lift-off processing face of MRF38 " (manufacture of polyester film company, Mitsubishi Chemical) is coated with above-mentioned composition, composition layer is arranged, and at this Release liner similar to the above is laminated in such a way that lift-off processing face becomes composition layer side on composition layer.

Then, illumination about 5mW/cm is irradiated from the two sides of laminated body²Ultraviolet light 3 minutes, solidify composition layer, formed The adhesive phase that 50 μm of thickness, obtaining having release liner/adhesive phase/release liner composition bonding sheet, (no substrate is viscous Close piece).The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.Thermal conductivity particle in adhesive phase containing than Example (particle volume ratio) is 42.9 volume %.

It should be noted that the glass transition temperature of the acrylic acid series polymeric compounds contained in adhesive phase is -62.8 ℃.In addition, the weight of the acrylic acid series polymeric compounds contained in adhesive phase is equivalent to the monomer for constituting above-mentioned slurries and multifunctional The total amount of monomer.

(embodiment 2)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 50 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 50 parts by weight as thermal conductivity particle, obtain composition, in addition to this with Embodiment 1 gets similarly bonding sheet (no substrate bonding sheet).The thickness (not including the thickness of release liner) of bonding sheet is 50 μ m.The content ratio of thermal conductivity particle in adhesive phase is 27.3 volume %.

(embodiment 3)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 50 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 200 parts by weight as thermal conductivity particle, obtain composition, in addition to this Bonding sheet (no substrate bonding sheet) is obtained similarly to Example 1.The thickness (not including the thickness of release liner) of bonding sheet is 50μm.The content ratio of thermal conductivity particle in adhesive phase is 48.5 volume %.

(embodiment 4)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 100 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 150 parts by weight as thermal conductivity particle, obtain composition, in addition to this Bonding sheet (no substrate bonding sheet) is obtained similarly to Example 1.The thickness (not including the thickness of release liner) of bonding sheet is 50μm.The content ratio of thermal conductivity particle in adhesive phase is 48.5 volume %.

(embodiment 5)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 125 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 125 parts by weight as thermal conductivity particle, obtain composition, in addition to this Bonding sheet (no substrate bonding sheet) is obtained similarly to Example 1.The thickness (not including the thickness of release liner) of bonding sheet is 50μm.The content ratio of thermal conductivity particle in adhesive phase is 48.5 volume %.

(embodiment 6)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 150 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 100 parts by weight as thermal conductivity particle, obtain composition, in addition to this Bonding sheet (no substrate bonding sheet) is obtained similarly to Example 1.The thickness (not including the thickness of release liner) of bonding sheet is 50μm.The content ratio of thermal conductivity particle in adhesive phase is 48.5 volume %.

(embodiment 7)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 200 parts by weight and trade name " HIGILITE the H-42 " (shape: broken as aluminium-hydroxide powder Broken shape, average grain diameter: 1 μm, Showa electrician corporation) 50 parts by weight as thermal conductivity particle, obtain composition, in addition to this with Embodiment 1 gets similarly bonding sheet (no substrate bonding sheet).The thickness (not including the thickness of release liner) of bonding sheet is 50 μ m.The content ratio of thermal conductivity particle in adhesive phase is 48.5 volume %.

(comparative example 1)

Thermal conductivity particle is not used completely, obtains bonding sheet (no substrate bonding sheet) similarly to Example 1 in addition to this. The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.The content ratio of thermal conductivity particle in adhesive phase is 0 Volume %.

(comparative example 2)

Add trade name " HIGILITE the H-42 " (shape: broken shape, average grain diameter: 1 μ as aluminium-hydroxide powder M, Showa electrician corporation) 250 parts by weight as thermal conductivity particle, obtain composition, in addition to this similarly to Example 1 To bonding sheet (no substrate bonding sheet).The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.In adhesive phase The content ratio of thermal conductivity particle is 48.5 volume %.

(comparative example 3)

Add trade name " HIGILITE the H-31 " (shape: broken shape, average grain diameter: 18 μ as aluminium-hydroxide powder M, Showa electrician corporation) 250 parts by weight as thermal conductivity particle, obtain composition, in addition to this similarly to Example 1 To bonding sheet (no substrate bonding sheet).The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.In adhesive phase The content ratio of thermal conductivity particle is 48.5 volume %.

(comparative example 4)

In 100 parts by weight of 2-EHA as monomer component, cooperate the quotient as Photoepolymerizationinitiater initiater The name of an article " Irgacure651 " (2,2- dimethoxy -1,2- diphenylethane -1- ketone, the manufacture of BASF JAPAN company) 0.05 parts by weight and trade name " Irgacure184 " (1- hydroxycyclohexylphenylketone, the manufacture of BASF JAPAN company) 0.05 weight Part is measured, then irradiates ultraviolet light until viscosity (BH viscosimeter No.5 rotor, 10rpm, 30 DEG C of measuring temperature) becomes about 20Pa S makes the mixture (partial polymer, the slurries of monomer mixture) of part polymerizing monomer components.

In above-mentioned 100 parts by weight of slurries, the dipentaerythritol hexaacrylate (trade name as polyfunctional monomer is added " KAYARAD DPHA-40H ", Japanese chemical drug corporation are made) 0.05 parts by weight and the trade name " PLYSURF as dispersing agent A212E " (manufacture of the first industrial pharmaceutical company) 1 parts by weight.Further, trade name of the addition as aluminium-hydroxide powder " HIGILITEH-31 " (shape: broken shape, average grain diameter: 18 μm, the manufacture of Showa electrician company) 125 parts by weight and as hydrogen The trade name " HIGILITE H-42 " (shape: broken shape, average grain diameter: 1 μm, the manufacture of Showa electrician company) of alumina powder 125 parts by weight obtain composition as thermal conductivity particle.

Release liner (trade name " the DIAFOIL of the polyethylene terephthalate of lift-off processing is implemented in single side The lift-off processing face of MRF38 " (manufacture of polyester film company, Mitsubishi Chemical) is coated with above-mentioned composition, composition layer is arranged, and at this On composition layer, release liner similar to the above is laminated in such a way that lift-off processing face becomes composition layer side.

Then, illumination about 5mW/cm is irradiated from the two sides of laminated body²Ultraviolet light 3 minutes, solidify composition layer, formed The adhesive phase that 50 μm of thickness, obtaining having release liner/adhesive phase/release liner composition bonding sheet, (no substrate is viscous Close piece).The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.Thermal conductivity particle in adhesive phase containing than Example (particle volume ratio) is 52 volume %.

It should be noted that the glass transition temperature of the acrylic acid series polymeric compounds contained in adhesive phase is -30 DEG C. In addition, the weight of the acrylic acid series polymeric compounds contained in adhesive phase is equivalent to the monomer and multifunctional list for constituting above-mentioned slurries The total amount of body.

(comparative example 5)

It is mixed as the monomer of monomer component being mixed with 90 parts by weight of 2-EHA, 10 parts by weight of acrylic acid It closes in object, cooperates trade name " Irgacure651 " (2,2- dimethoxy -1,2- diphenyl second as Photoepolymerizationinitiater initiater Alkane -1- ketone, the manufacture of BASF JAPAN company) 0.05 parts by weight and trade name " Irgacure184 " (1- hydroxy-cyclohexyl benzene Base ketone, the manufacture of BASFJAPAN company) 0.05 parts by weight, then irradiate ultraviolet light until viscosity (BH viscosimeter No.5 rotor, 30 DEG C of 10rpm, measuring temperature) become about 20Pas, the mixtures of production part polymerizing monomer components be (monomer mixture Partial polymer, slurries).

In above-mentioned 100 parts by weight of slurries, the dipentaerythritol hexaacrylate (trade name as polyfunctional monomer is added " KAYARAD DPHA-40H ", Japanese chemical drug corporation are made) 0.05 parts by weight and the trade name " PLYSURF as dispersing agent A212E " (manufacture of the first industrial pharmaceutical company) 1 parts by weight.Further, trade name of the addition as aluminium-hydroxide powder " HIGILITEH-31 " (shape: broken shape, average grain diameter: 18 μm, the manufacture of Showa electrician company) 125 parts by weight and as hydrogen The trade name " HIGILITE H-42 " (shape: broken shape, average grain diameter: 1 μm, the manufacture of Showa electrician company) of alumina powder 125 parts by weight obtain composition as thermal conductivity particle.

Release liner (trade name " the DIAFOIL of the polyethylene terephthalate of lift-off processing is implemented in single side The lift-off processing face of MRF38 " (manufacture of polyester film company, Mitsubishi Chemical) is coated with above-mentioned composition, composition layer is arranged, and at this On composition layer, release liner similar to the above is laminated in such a way that lift-off processing face becomes composition layer side.

Then, illumination about 5mW/cm is irradiated from the two sides of laminated body²Ultraviolet light 3 minutes, solidify composition layer, formed The adhesive phase that 50 μm of thickness, obtaining having release liner/adhesive phase/release liner composition bonding sheet, (no substrate is viscous Close piece).The thickness (not including the thickness of release liner) of bonding sheet is 50 μm.Thermal conductivity particle in adhesive phase containing than Example (particle volume ratio) is 48.5 volume %.

It should be noted that the glass transition temperature of the acrylic acid series polymeric compounds contained in adhesive phase is 5 DEG C.Separately Outside, the weight of the acrylic acid series polymeric compounds contained in adhesive phase is equivalent to the monomer and polyfunctional monomer for constituting above-mentioned slurries Total amount.

(evaluation)

Following measurements or evaluation are carried out to bonding sheet obtained in embodiment and comparative example.And it the results are shown in table 1.

(1) 50 μm of screening characteristics

The homogeneity of the thickness of the adhesive phase of bonding sheet obtained in visual confirmation the above embodiments and comparative example is glued The situation that the thickness of adhesive phase is uniform and adhesive layer surface is smooth is evaluated as " good by the surface smoothness of mixture layer (zero) ", by the uneven thickness of adhesive phase one or adhesive layer surface see thin-walled spot (generation there are the position of adhesive phase, Be not present adhesive phase position) the case where be evaluated as " bad (×) ".

(2) 180 ° of peel adhesions

The tape sheet of cut-out length 100mm, width 20mm from bonding sheet obtained in above-described embodiment and comparative example, system The tape sheet of growth strip.It should be noted that each tape sheet with a thickness of the thickness recorded in above-described embodiment and comparative example.

Then, release liner is removed from the tape sheet of above-mentioned strip, by making 2kg under 23 DEG C, 50%RH atmosphere Round-trip 1 time of roller and adhesive surface (aspect of measure) is crimped on SUS304 steel plate, production measurement sample.

After said determination sample is placed 30 minutes in 23 DEG C, the atmosphere of 50%RH, cupping machine (trade name is used The manufacture of " TCM-1kNB ", Minebea company) 180 ° of disbonded tests are carried out, measure 180 ° of peel adhesions to SUS304 steel plate (180 ° of peel adhesions) (N/20mm).It measures under 23 DEG C, the atmosphere of 50%RH, with 180 ° of peel angle, tensile speed 300mm/ minutes conditions carry out.

(3) thermal conductivity

For bonding sheet obtained in the above embodiments and comparative example, thermal characteristics evaluating apparatus pair shown in FIG. 1 is used The thermal conductivity of thickness direction implements measurement.(a) of Fig. 1 is the front schematic view of thermal characteristics evaluating apparatus, and (b) of Fig. 1 is that heat is special The side schematic view of property evaluating apparatus.It should be noted that removing release liner in measurement.

Specifically, one of the aluminum (A5052, thermal conductivity: 140W/mK) in the cube for being formed as a side length 20mm To block (sometimes referred to as " barred body ".) bonding sheet 1 (wide: 20mm, length: 20mm) is sandwiched between L, by a pair of of block L bonding sheet 1 Fitting.

Then, (existed in such a way that a pair of of block L presents lower placement in heater (heat block) H and radiator with cooling water The cooling substrate that constitutes of mode of inside circulation) a pair of block is configured between C.Specifically, the top of the block L in upside Heater H is configured, the lower section of block L configures radiator C in downside.

At this point, being located at a pair of of pressure adjustment use through heater H and radiator C with a pair of of block L that bonding sheet 1 is bonded Between screw T.It should be noted that in pressure adjustment with dynamometer R is configured between screw T and heater H, can survey Surely the mode for screwing pressure of the pressure adjustment with screw T when is constituted, and uses the pressure as the pressure for being applied to bonding sheet 1.

Specifically, in this experiment, screwing pressure adjustment screw T until the pressure for being applied to bonding sheet 1 reaches 25N/cm²(250kPa)。

In addition, 3 of contact displacement meter are arranged in a manner of from block L and bonding sheet 1 of the side radiator C through downside It pops one's head in P (diameter 1mm).At this point, constituting as follows: the upper end for the P that pops one's head in is in the following table face contact of the block L with upside State, the interval (thickness of bonding sheet 1) between upper and lower block L can be measured.

The mounting temperature sensor D on heater H and upper and lower block L.Specifically, installing temperature at the 1 of heater H Sensor D is spent, mounting temperature sensor D is distinguished with the interval 5mm in the up-down direction at the 5 of each block L.

Measurement is following to be carried out: firstly, pressure adjustment is screwed with screw T, applying pressure to bonding sheet 1, by heater H's Temperature is set in 80 DEG C, and makes to recycle 20 DEG C of cooling water in radiator C.

Then, after the temperature of heater H and upper and lower block L are stablized, with the block above and below each temperature sensor D measurement The temperature of L is calculated the heat flux (hot-fluid for passing through bonding sheet 1 by the thermal conductivity (W/mK) and temperature gradient of upper and lower block L Beam), and calculate the temperature at the interface of upper and lower block L and bonding sheet 1.Then, using these parameters, using following thermally conductive Rate equation (Fourier's law) calculates thermal conductivity (W/mK) and thermal resistance (cm under the pressure²·K/W)。

Q=- λ gradT

R=L/ λ

Q: the heat flux of per unit area

GradT: temperature gradient

L: the thickness of piece

λ: thermal conductivity

R: thermal resistance

(4) anti-flammability

Based on flame retardant test standard UL94, flame retardant test below is carried out.

The bonding sheet as obtained in above-described embodiment and comparative example obtains the test film of 5 length 200mm, width 50mm. It should be noted that each tape sheet with a thickness of the thickness recorded in above-described embodiment and comparative example.By the one of above-mentioned test film Hold vertical hanging.Then, make another end in contact flame 3 seconds using burner, temporarily far from after flame, confirmation is contacted again flame The case where state of test film after 3 seconds evaluates anti-flammability, will meet benchmark X below is evaluated as " VTM-0 ", will be unsatisfactory for " poor (×) " is evaluated as in the case where benchmark X.

Benchmark X: (i) below~(v) all meets.

(i) flaming combustion time (burning time after contacting initial flame and the flame for contacting the 2nd time of each test film Burning time afterwards adds up to) within 10 seconds.

(ii) total ascent time of the flaming combustion time of 5 test films is within 50 seconds.

(iii) total ascent time of the flaming combustion time of each test film after the 2nd contact flame and glowing time Within 30 seconds.

(iv) in 5 test films, the cotton configured in lower section is not made to catch fire due to the droppings that burns is fallen from test film Test film.

(v) unburned to suspension (hanging げ under り) part (upper part) in all test films.

(5) retentivity

Using bonding sheet obtained in the above embodiments and comparative example as evaluation sample, according to the holding of JIS Z1528 The evaluation of power carries out.Had in the single side of bonding sheet using TORAY corporation " Lumirror (Le ミ ラ ー) S-10#25 " There is the sample of lining material.Pasted with 2kg roller with round-trip 1 time so that the sample with lining material reach 10mm × The area of 20mm, behind room temperature curing 30 minutes of 23 DEG C, the load 1 for applying 100g (or 300g) under 80 DEG C of atmosphere is small When, the displacement that confirmation Self-adhesive initial stage starts, as the value of retentivity (mm).

Symbol description

1 bonding sheet

2 thermometers

3 contact displacement meters

C radiator

D temperature sensor

H heater (heat block)

L block (barred body)

P probe

R dynamometer

Screw is used in the adjustment of T pressure

Claims (5)

1. a kind of no substrate thermal conductivity double-sided adhesive sheet, with adhesive phase, and described adhesive layer with a thickness of 50 μm Hereinafter, in described adhesive layer, the grain of 12 μm~25 μm of D50 average grain diameter of 0.1 μm~3 μm of particle group A and D50 average grain diameter Subgroup B is cooperated as thermal conductivity particle with the ratio between the particle group A and particle group B for the ratio of 2:8~8:2, the ratio For weight ratio, described adhesive layer is under 23 DEG C, 50%RH, tensile speed 300mm/min, 180 ° of peel angle of stripping conditions 180 ° of peel adhesions to SUS304 steel plate are 2.5N/20mm or more；The thermal conductivity double-sided adhesive sheet is in UL94 standard With the anti-flammability of VTM-0 or V-0 in flame retardant test.

2. thermal conductivity double-sided adhesive sheet according to claim 1, wherein thermal conductivity particle in described adhesive layer contains Amount is 25 volume % or more and 75 volume % or less.

3. thermal conductivity double-sided adhesive sheet according to claim 1 or 2, thermal conductivity is 0.3W/mK or more.

4. thermal conductivity double-sided adhesive sheet according to claim 1 or 2, the retentivity at 80 DEG C, 300gf be 2mm with Under.

5. thermal conductivity double-sided adhesive sheet according to claim 1 or 2, wherein described adhesive layer is active energy beam Curing adhesive layer.