CN100386375C - Resin composition for thermally conductive material and thermally conductive material - Google Patents

Abstract

A resin composition for thermally conductive materials which comprises a polymer (I), a liquid plasticizer (II), and a thermally conductive filler (III) having a thermal conductivity of 20 W/m.K or higher, characterized in that the liquid plasticizer (II) is liquid at 25 DEG C and has a percentage loss of weight through 24-hour holding at 130 DEG C of 2 wt.% or smaller. A thermally conductive material excellent in thermal conductivity and flexibility could be obtained from the resin composition for thermally conductive materials.

Description

Thermally conductive materials resin combination and thermally conductive materials

Technical field

The present invention relates to a kind of resin combination that for example is used for obtaining at the thermally conductive materials of the employed thermal conductivity thin slice of heat radiation purposes etc., in more detail, the thermally conductive materials resin combination that relate to thermal conductivity, flexibility, has excellent formability.

Background technology

Make the resin combination that in having the resin of flexibility, cooperates the thermal conductivity weighting agent of raising such as aluminum oxide, silicon-dioxide thermal conductivity for example to form, laminar (thermal conductivity thin slice) object of solidifying formation takes place, for example be used for following purposes, promptly, make the Heating element of this sheet members that obtains built-in electric, electronic unit etc. in various electric products such as PC or plasma display and for example between the radiators such as scatterer, radiator element, metallic heat radiating plate, in the purposes that the heating of electric, electronic unit etc. is dispelled the heat, use.Usually the air spots of Heating element or radiator is sliding under most situation, increases in order to make the contact area between them, improves from the heat transfer efficiency of Heating element to radiator, so require the thermal conductivity thin slice to have flexibility.

All the time,, use silicone rubber or silicon gel, but there is the price height in these resins, needs the time during curing and productivity is low, cause problems such as the contact of electronic unit is bad because of producing low-molecular-weight siloxanes in addition as resin with flexibility.

In order to address the above problem, to study to make and containing second-order transition temperature and be multipolymer below-30 ℃ and monomeric tackiness agent with unsaturated link(age) heat radiation (thermal conductivity) thin slice (for example, the spy opens 2001-335602 number) after solidifying.Also have, also in addition research to contain to have carbonatoms be that the acrylate monomer of 2～18 alkyl is the resin composition for radiating material (for example, the spy opens 2002-155110 number) of the non-silicon system of the polymerizable monomer of principal constituent and Photoepolymerizationinitiater initiater and thermal conductivity weighting agent.But, in these inventions, because do not use silicone rubber or silicon gel, although can improve the bad problem of contact by the caused electronic unit of generation of low-molecular-weight siloxanes, but what the inventor etc. studied found that, room for improvement is arranged aspect the flexibility of plasticity when the thermal conductivity thin slice is formed or the thin slice that obtains.

Become the thermal softening agent of liquid, the thermal conductivity thin slice of thermal conductivity weighting agent (for example, the spy opens 2002-234952 number) when on the other hand, disclosing under high-molecular gel, the normal temperature such as for example containing acrylic gel to solid or gluey the heating.But these thermal conductivity thin slices have room for improvement aspect flexibility.

In addition, known have an acrylic acid series carbamate resins that obtains from the acrylic acid series urethane resin compositions, wherein said acrylic acid series urethane resin compositions is to obtain (for example, the spy opens 2002-30212 number) from acrylic acid oligomer that has 2 hydroxyls a molecule and the multi-functional isocyanic ester that has 2 isocyanate group in a molecule at least.

But, when these resins are used for the manufacturing of thermal conductivity thin slice, think to have following great number of issues, that is, and the composition viscosity height that obtains and operability is poor; Because of the height that can't realize the thermal conductivity weighting agent cooperates, so the thermal conductivity of the thermal conductivity thin slice that obtains reduces; Be evenly dispersed in the thermal conductivity weighting agent in the resin and to carry out the mixing required time longer, thereby cause the productivity variation; And then when making composition, be blended in the composition the deaeration deterioration of air, therefore in the heat radiation thin slice that obtains, produce bubble, thus plasticity, heat conductivility deterioration etc.

And then, known have for example contain as the coating of the organometallics of urethane reaction catalyzer and acidic substance with resin combination (for example, the spy opens 2001-240797 number) with urethane bond.But, in the document, there is not the record of relevant thermally conductive materials, the interpolation of acidic substance is also just as prolonging by the carbamate crosslinking reaction and the effect of the technology of the serviceable time of solidified coating composition.The record that hardness during in addition, not about exposure under long-time high temperature reduces.

But, (spy opens 2003-49144 number (methyl) acrylic resin as the base resin of thermally conductive materials mostly, above-mentioned spy opens 2002-155110 number, Te Kaiping 11-269438 number etc.), but should (methyl) acrylic resin be mostly form with the polymkeric substance that mixed (methyl) acrylic acid series and monomeric liquid resin composition (being called the vinylformic acid paste) be provided (for example, Te Kaiping 9-67495 number etc.), user and then utilize thermopolymerization (radical polymerization) or linking agent to make this liquid resin composition that crosslinked (curing) take place and form latticed structure becomes (methyl) acrylic resin final product (molding thus, thin slice etc.).In addition, also know and use special catalyzer manufacturing (methyl) acrylic resin (spy open 2000-128911 number etc.).

Known such vinylformic acid paste for example carries out polymerization to (methyl) acrylic monomer in toluene, after removing toluene, make aqueous resin (paste) by appending (methyl) acrylic monomer, utilize polymerization starter to make this paste polymerization (the above-mentioned spy of reference opens flat 9-67495 number embodiment 7～9 etc.).In addition, open in 2003-49144 number, in vinyl acetic monomer, (methyl) acrylic monomer is carried out radical polymerization, be coated to and carry out drying on the PET film afterwards above-mentioned spy.But (methyl) acrylic resin that utilizes these methods to obtain contains solvent (toluene, vinyl acetic monomer etc.).That is, in these methods, desolvate, can not remove fully and desolvate although remove midway.When using (methyl) acrylic resin that so obtains, even also worry volatilize residual solvents on a small quantity at every turn, particularly this worries to increase in the purposes (thermally conductive materials etc.) of heating.

Summary of the invention

The objective of the invention is to, solve above-mentioned prior art problems, the thermally conductive materials swimming resin combination and the long-time excellent thermal conductivity and the thermally conductive materials of flexibility of showing that have excellent formability are provided.

The present invention relates to a kind of thermally conductive materials resin combination, be to contain the thermally conductive materials resin combination that polymkeric substance (I), aqueous softening agent (II) and thermal conductivity are the above thermal conductivity weighting agent (III) of 20W/mK, above-mentioned aqueous softening agent (II) 25 ℃ down for liquid and when maintenance under 130 ℃ in the time of 24 hours its rate of mass reduction be below the 2 quality %.

Embodiment

Thermally conductive materials of the present invention is meant that with resin combination (being designated hereinafter simply as resin combination) containing polymkeric substance (I), aqueous softening agent (II) and thermal conductivity is the material of the above thermal conductivity weighting agent (III) of 20W/mK.By this resin combination is solidified, obtain in the crosslinked grid of polymkeric substance (I), having kept the cured article with flexibility of aqueous softening agent (II), this cured article becomes thermally conductive materials.In addition, in this manual, the compound group of additional distinct symbols is just represented different compound groups unless otherwise specified.

At first, the aqueous softening agent (II) as the necessary composition of resin combination of the present invention is described.This aqueous softening agent (II) is down liquid at 25 ℃, is not mix with water and can be with the compound of polymkeric substance (I) plasticized.Above-mentioned aqueous softening agent (II) is because will show the flexibility of the cured article of the resin combination that obtains long-term and stably, so preferably use the high material of thermotolerance.In addition, as the thermotolerance benchmark, in the present invention, use under 130 ℃ of temperature the rate of mass reduction (%) [the preceding quality of=100 * (quality after quality-maintenances before keeping)/maintenance] after aqueous softening agent (II) kept 24 hours.Using this rate of mass reduction in the present invention is the following aqueous softening agent (II) of 2 quality %.This rate of mass reduction more preferably below the 1 quality %, more preferably below the 0.5 quality %, most preferably is below the 0.1 quality %.In addition, this rate of mass reduction is for example obtained by putting into the aqueous softening agent about several g and be determined at the quality of preserving under 130 ℃ the atmosphere before and after 24 hours in the container of refractory materialss such as aluminium.

In addition, as aqueous softening agent (II), low viscosity also is preferred condition.For example, the viscosity under 25 ℃ of the use temperatures be 1000mPas following, more preferably 800mPss following, more preferably 500mPas following, be preferably the softening agent of 300mPas about following especially.In addition, the viscosity of aqueous softening agent (II) for example can use the Brookfield viscometer of (strain) Tokyo gauge system to measure.Following table 1 be expression in this Brookfield viscometer rotor No. and the combination of rotating speed, with the table of the relation of the higher limit of the viscosity that can measure, actual mensuration viscosity is more near its higher limit, error at measurment just can be more little.When judging roughly the viscosity of determination object in advance, on one side with reference to this table 1, the rotor No. that decision is on one side used and the combination of rotating speed.On the other hand, under the situation that viscosity is roughly failed to understand, rotor No. is changed from the little side of a big direction, in addition, rotating speed is changed from low speed side to high-speed side, measure in the scope in appropriateness in the relation of considering following table 1.

Table 1

	Rotating speed 60rpm	Rotating speed 30rpm	Rotating speed 12rpm	Rotating speed 6rpm
					Rotor No.1	100mPa·s	200mPa·s	500mPa·s	1000mPa·s
Rotor No.2	500mPa·s	1000mPa·s	2500mPa·s	5000mPa·s
					Rotor No.3	2000mPa·s	4000mPa·s	10000mPa·s	20000mPa·s
Rotor No.4	10000mPa·s	20000mPa·s	50000mPa·s	100000mPa·s

As the object lesson of aqueous softening agent (II), can enumerate phthalic ester and be softening agent, Pyromellitic Acid ester and be softening agent, trimellitate and be softening agent, adipic acid ester and be softening agent, polyester and be softening agent, epoxy and be softening agent, phosphoric acid ester and be softening agent, rubber with softening agent etc.Two or more kinds may be used for they.

Excellent heat resistance and the softening agent that satisfies the condition of above-mentioned rate of mass reduction are selected from the have aromatic ring aqueous softening agent of (particularly phenyl ring) mostly, for example, as phthalate, as didecyl phthalate, phthalic acid two (undecyl ester), phthalic acid two phthalic acid two C such as (dodecyl esters) _5～15Alkyl esters (preferred phthalic acid two C _9～15Alkyl esters) etc. more suitable.In addition, as the trimellitate class, as trimellitic acid three C such as trioctyl trimellitate, tri trimellitate ester in the ninth of the ten Heavenly Stems, tri trimellitate esters in the last of the ten Heavenly stems _7～14Alkyl esters (preferred tri trimellitate C _{8～ 12}Alkyl esters) etc. more suitable.As the pyromellitic ester class, as pyromellitic acid such as tetraoctyl 1,2,4,5-benzenetetra-carboxylate four C _6～13Alkyl esters (preferred pyromellitic acid four C _7～10Alkyl esters) etc. more suitable, as phosphoric acid ester, as tricresyl phosphate biphenyl ester, tricresyl phosphate (toluene ester), tricresyl phosphate (diformazan phenyl ester) etc., on phenyl ring, C can be arranged _1～3Tricresyl phosphate (phenyl ester) class that alkyl replaces is more suitable.

As above-mentioned aqueous softening agent (II), can use commercially available material, for example can the illustration phthalate ester decanoate [the PVC ニ サ イ ザ 1 of flower king (strain) system etc.], phthalic acid two C _10～12Alkyl ester [the PVC ニ サ イ ザ 1 of flower king (strain) system etc.], tri trimellitate 2-ethylhexyl trimellitate [the ト リ メ of flower king (strain) system _StarNetwork ス T-08 etc.], trioctyl trimellitate [rising sun electrochemical industry (strain) system ア デ カ サ イ ザ one C-8 etc.], tri trimellitate n-octyl [the ト リ メ of flower king (strain) system _StarNetwork ス N-08, ト リ メ _StarNetwork ス New-NSK; ア デ カ サ イ ザ one C-880 of rising sun electrochemical industry (strain) system etc.], triisononyl trimellitate [ア デ カ サ イ ザ one C-9N of rising sun electrochemical industry (strain) system etc.], tri trimellitate isodecyl trimellitate [the ト リ メ of flower king (strain) system _StarNetwork ス T-10; ア デ カ サ イ ザ one C-10 of rising sun electrochemical industry (strain) system etc.], trimellitic acid mixed alcohol ester [ア デ カ サ イ ザ one C-79, ア デ カ サ イ ザ one C-810 etc. of rising sun electrochemical industry (strain) system], tetraoctyl 1,2,4,5-benzenetetra-carboxylate [ア デ カ サ イ ザ one UL-80 of rising sun electrochemical industry (strain) system etc.], pyromellitic acid mixed alcohol ester [ア デ カ サ イ ザ one UL-100 of rising sun electrochemical industry (strain) system etc.], tricresyl phosphate biphenyl ester [the Network ロ ニ テ of aginomoto Off ア イ Application テ Network ノ (strain) system _StarNetwork ス CDP etc.], tricresyl phosphate (toluene ester) [the Network ロ ニ テ of aginomoto Off ア イ Application テ Network ノ (strain) system _StarNetwork ス TCP etc.], tricresyl phosphate (diformazan phenyl ester) [the Network ロ ニ テ of aginomoto Off ア イ Application テ Network ノ (strain) system _StarNetwork ス TXP etc.] etc.These aqueous softening agent (II) can use separately, can also make up more than 2 kinds and use.

Then, the polymkeric substance (I) that contains in the resin combination of the present invention is described.(methyl) acrylic acid polymer (I-a) and bridging property polymkeric substance (I-b) are arranged in polymkeric substance (I).When polymkeric substance (I) was (methyl) acrylic acid polymer (I-a), the preferred resin composition contained polymerizable monomer (IV).

(methyl) acrylic acid polymer (I-a) is meant that 50 quality % of structural unit above (being preferably more than the 70 quality % and then more than the preferred 80 quality %) are the polymkeric substance of (methyl) acrylate.In addition, " metha crylic polymer " be meant in above-mentioned (methyl) acrylate surpass 50 quality % be the polymkeric substance of methacrylic ester, " acrylic acid polymer " is meant and is the polymkeric substance of acrylate in above-mentioned (methyl) acrylate more than the 50 quality %.In addition, in polymkeric substance, also contain multipolymer more than 2 yuan.

As the monomer that is used for making (methyl) acrylic acid polymer (I-a), can be fit to use material that the alkyl of (methyl) esters of acrylic acid, (methyl) alkyl-acrylates replaced by functional group's (for example, carboxyl, hydroxyl etc.) etc.As (methyl) alkyl-acrylates, for example can enumerate (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid myristin, (methyl) stearyl acrylate acyl ester etc.Above-mentioned (methyl) alkyl-acrylates be not limited to alkyl be the straight chain shape (just, normal), can also be a chain, for example abnormal shape or low alkyl group (for example replace, carbonatoms is about 1～3 alkyl) [for example, (methyl) EHA etc.].

Wherein, because the flexibility of the cured article of resin combination (thermally conductive materials) is improved, (methyl) alkyl-acrylates that so the carbonatoms of preferred alkyl part (under the situation that low alkyl group replaces, total carbonatoms) is about 2～18 (more preferably about 3～15).These monomers can use separately, can also make up a plurality of uses.When a plurality of these monomers of combination, can make up a plurality of (methyl) alkyl acrylate, for example, can and contain functional group's (methyl) acrylate with (methyl) alkyl-acrylates and (methyl) Hydroxyethyl acrylate or (methyl) vinylformic acid etc.Such when containing functional group's (methyl) acrylate when using, (methyl) acrylic acid polymer (I-a) that obtains improves for the wettability of thermal conductivity weighting agent (III) etc.Use such (methyl) acrylic acid polymer (I-a) that functional group's (methyl) acrylate obtains that contains, also can be called as bridging property polymkeric substance described later (I-b), but improve effect etc. in order to bring into play wettability, can't consume functional group by crosslinked the grade, so in the resin combination that has used (methyl) acrylic acid polymer (I-a), do not add linking agent (VI).

When making (methyl) acrylic acid polymer (I-a), in the monomer component 100 quality % that constitute (methyl) acrylic acid polymer (I-a), the preferred carbonatoms that uses alkyl is more than (methyl) alkyl acrylate 50 quality of 2～18, more preferably more than the 70 quality %, most preferably be more than the 80 quality %.The flexibility of the thermally conductive materials after the curing can be improved, heat transfer area can also be improved and the tracing ability of adherend.In addition, can suppress the usage quantity of softening agent, so also show the effect of oozing out that suppresses softening agent.

The second-order transition temperature of (methyl) acrylic acid polymer (I-a) is preferably below 0 ℃, more preferably-30 ℃ below, more preferably-40 ℃ below.If surpass 0 ℃, the flexibility of the cured article of the resin combination that then obtains is abundant inadequately sometimes.In addition, the second-order transition temperature of (methyl) acrylic acid polymer (I-a) can use differential scanning calorimetry to adopt ordinary method to measure.

The molecular weight of (methyl) acrylic acid polymer (I-a) is being in 10,000～1,000,000 the scope by the weight-average molecular weight based on the polystyrene conversion of gel permeation chromatography (GPC) preferably, more preferably in 30,000～800,000 the scope, most preferably be in 50,000～500,000 the scope.When weight-average molecular weight less than 10,000 the time, performances such as the solvent resistance of the cured article of the resin combination that obtains or thermotolerance reduce, on the other hand, when weight-average molecular weight surpasses 1,000,000, the viscosity of (methyl) acrylic acid polymer (I-a) that obtains self raises, and the operation when sometimes resin combination being shaped causes damage.

At polymkeric substance (I) is under the situation of above-mentioned (methyl) acrylic acid polymer (I-a), and resin combination preferably contains polymerizable monomer (IV).This is to improve plasticity because reduce the viscosity of resin combination.Polymerization takes place by the radical polymerization initiator (V) that added in this polymerizable monomer (IV) before curable resin composition, have the effect of the resin combination of making solidified.

When polymerizable monomer (IV) is 100 quality % in the total amount of (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV), preferably being adjusted to (methyl) acrylic acid polymer (I-a) is 10～80 quality %, and polymerizable monomer (IV) is 20～90 quality %.Preferred ratio is, (methyl) acrylic acid polymer (I-a) is 15～70 quality %, and polymerizable monomer (IV) is 30～85 quality %; Most preferred ratio is, (methyl) acrylic acid polymer (I-a) is 30～60 quality %, and polymerizable monomer (IV) is 40～70 quality %.When (methyl) acrylic acid polymer is that polymerizable monomer (IV) is when surpassing 90 quality % less than 10 quality %, after mixing with the thermal conductivity weighting agent, for example separating of resin and thermal conductivity weighting agent when being pre-formed into sheet or when being shaped appear, so not preferred; When (methyl) acrylic acid polymer surpasses 80 quality % is that polymerizable monomer (IV) is during less than 20 quality %, the viscosity of resin combination becomes too high, so the deterioration of the surface smoothing of the thin slice that obtains when the reduction of appearance operation, for example preliminary shaping, the deterioration of the surface smoothing when being shaped be not preferred.

As this polymerizable monomer (IV), just be not particularly limited so long as have the monomer of 1 free-radical polymerised pair of key, wherein preferred the carbonatoms of illustrative alkyl is (methyl) alkyl acrylate of 2～18 as being used for making the material of (methyl) acrylic acid polymer (I-a).Two or more kinds may be used for they.The carbonatoms of these alkyl is the usage quantity of (methyl) alkyl acrylate of 2～18, is more than the 80 quality % in polymerizable monomer (IV) composition 100 quality %.

In addition, as required, also can in the part of polymerizable monomer (IV), use the monomer that has free-radical polymerised pair of key more than 2 in 1 molecule (below, be called polyfunctional monomer).By using polyfunctional monomer, and then obtain the cured article of thermotolerance or resistance to chemical reagents, creep (creep) property excellence, so determine whether to use according to the performance that requires of cured article.The usage quantity of polyfunctional monomer when the total amount with (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV) is made as 100 quality %, is preferably below 5 mass parts, more preferably below 4 mass parts, more preferably below 3 mass parts.When the polyfunctional monomer amount surpassed 5 mass parts, the flexibility of the cured article of the resin combination that obtains sometimes reduced.

As the concrete example of polyfunctional monomer, can enumerate multi-functional (methyl) acrylic monomer, Vinylstyrene, diallyl phthalate, triallyl cyanurate etc.In above-mentioned multi-functional (methyl) acrylic monomer, comprise (gathering) two (methyl) vinylformic acid glycol ester, poly-two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid 1,4-butanediol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1, two (methyl) esters of acrylic acid (preferred two (methyl) vinylformic acid C such as 6-hexylene glycol ester _2～6Alkane diol ester); Three (methyl) esters of acrylic acids such as trimethylolpropane tris (methyl) acrylate; Four (methyl) esters of acrylic acids such as four (methyl) vinylformic acid pentaerythritol ester; The condenses of six (methyl) vinylformic acid dipentaerythritol ester etc. above-mentioned two, three and/or four (methyl) esters of acrylic acid etc.Above-mentioned multi-functional polymerizable monomer can use separately, can also make up more than 2 kinds and use.

Above-mentioned (methyl) acrylic acid polymer (I-a) can use the above-mentioned raw materials monomer to adopt known free radical polymerisation process such as mass polymerization, solution polymerization, letex polymerization to carry out polymerization and obtain.In mass polymerization, stop the partially polymerized method of polymeric halfway if adopt, then can obtain the mixture of polymkeric substance (I-a) and polymerizable monomer (IV), so easy and preferred with 1 operation.Certainly, can in this mixture, add polymerizable monomer (IV) in addition and adjust.In addition, can adopt solution polymerization process or emulsion polymerization, the polymerization of (methyl) acrylic acid polymer (I-a) is finished after, make volatilizations such as moisture and solvent, add polymerizable monomer (IV).

In addition, can be in the presence of aqueous softening agent (II), the starting monomer of polymerization (methyl) acrylic acid polymer (I-a).Compare easier controlled polymerization speed with mass polymerization, and can suppress impurity such as moisture or solvent and be blended in the resin combination.At this moment, after making the whole polymerizations of (methyl) acrylic acid polymer (I-a), add polymerizable monomer (IV) in addition, can also further add aqueous softening agent (II) as required.In addition, can finish the polymerization of the starting monomer of (methyl) acrylic acid polymer (I-a) halfway, if this method, can obtain the mixture of (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV) and aqueous softening agent (II) with 1 operation.Certainly, also can in this mixture, add polymerizable monomer (IV) or aqueous softening agent (II) in addition and adjust proportioning.

When polymerization, use radical polymerization initiator.With regard to this radical polymerization initiator, can with add the resin combination that contains (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV) in addition in identical so that make polymerizable monomer (IV) that polymeric radical polymerization initiator (V) take place, also can be different, but consume because be aggregated reaction, so add polymerization starter (V) in the resin combination in suitable period in addition the reaction back.

In above-mentioned azo series initiators, for example comprise 2,2 '-Diisopropyl azodicarboxylate, dimethyl-2, two (2 Methylpropionic acid ester) classes of 2 '-azo, 2-phenylazo-2,4-dimethyl-4-methoxyl group valeric acid nitrile etc.

In above-mentioned organo-peroxide, for example comprise peroxidation ketones such as methylethyl ketone peroxide; Hydroperoxide type such as cumene hydroperoxide; Superoxide such as benzoyl peroxide, lauroyl peroxide two acyl classes; Dialkyl peroxide classes such as dicumyl peroxide; 1,1-di-t-butyl peroxide-3,3, ketal peroxide classes such as 5-trimethyl-cyclohexane; Peroxidation tert-pentyl-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, peroxidation tert-pentyl-3,5,5-tri-methyl hexanoic acid ester, 1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate, 1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-3,5, alkyl super-acid ester classes such as 5-tri-methyl hexanoic acid ester, t-butylperoxy pivarate; BPIC (t butyl peroxy isopropyl carbonate), t-butyl peroxy-2-ethylhexyl carbonic ether, 1, peroxocarbonate classes such as two (the t-butyl peroxy ketonic oxygen base) hexanes of 6-etc.

With regard to the usage quantity of radical polymerization initiator, as long as (methyl) esters of acrylic acid generation radical polymerization just is not particularly limited, can suitably set according to the kind of radical polymerization initiator, for example with respect to starting monomer 100 mass parts, be about 0.01～1 mass parts, be preferably about 0.05～0.7 mass parts, more preferably about 0.10～0.5 mass parts.And radical polymerization initiator can suitably be cut apart as required and add, and can dilute the back with aqueous softening agent (II) in addition and add.

When polymerization, can use chain-transfer agent as required.As chain-transfer agent, can use known various chain-transfer agent, for example can enumerate α-Jia Jibenyixierjuwu, tetracol phenixin, mercaptan compound (for example, n-dodecane mercaptan etc.) etc.The usage quantity of chain-transfer agent suitably determined, but with respect to starting monomer 100 mass parts, for example is about 0.01～2 mass parts, is preferably about 0.05～1.5 mass parts, more preferably about 0.10～1 mass parts.

Temperature of reaction also can suitably be set, for example be mostly from about 40～150 ℃, preferably set from about 50～100 ℃ scope.

At polymkeric substance (I) is under the situation of (methyl) acrylic acid polymer (I-a), preferably contains polymerizable monomer (IV) and radical polymerization initiator (V) in resin combination.Because the existence of polymerization starter (V) can make resin combination solidify rapidly, improves the productivity of thermally conductive materials.As radical polymerization initiator (V), except above-mentioned known in the past thermal polymerization, can also use light trigger etc.For example make by heat under the resin combination solidified situation, use thermal polymerization to be cured and get final product, in addition, under by the situation that for example ultraviolet ray is cured, can use Photoepolymerizationinitiater initiater to be cured and get final product, can suitably select according to curing.Wherein, utilize heat make the employed solidification equipment of resin combination solidified method easy and aspect cost excellence, more preferably use thermal polymerization that resin combination is solidified.Can use known curing catalyst, the curing of the effect that is used to promote thermal polymerization to promote auxiliary agent.These thermal polymerizations are preferably 0.1～5 mass parts with respect to total 100 mass parts of (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV), preferred consolidation promotor is 0.05～3 mass parts, solidifies to promote that auxiliary agent is preferably 0.05～2 mass parts.

In polymkeric substance (I) is resin combination under (methyl) acrylic acid polymer (I-a) situation, when the total amount of aqueous softening agent (II) and (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV) is 100 quality %, preferably aqueous softening agent (II) is adjusted to 5～60 quality % (more preferably 15～40 quality %), (methyl) acrylic acid polymer (I-a) is adjusted to 10～60 quality % (more preferably 10～50 quality %), polymerizable monomer (IV) is adjusted to 30～85 quality % (more preferably 40～65 quality %).

Under the situation of aqueous softening agent (II) less than 5 quality %, the hardness of the cured article of the resin combination that obtains might increase and can't obtain the flexibility of necessity in thermally conductive materials; Surpass under the situation of 60 quality % at aqueous softening agent (II), the flexibility of the cured article of the resin combination that obtains increases, and aqueous softening agent (II) might occur and separate from cured article.

Under the situation of (methyl) acrylic acid polymer (I-a) less than 10 quality %, when for example from the resin combination that obtains when the thermal conductivity thin slice is shaped, might appear separating of resin and other compositions, surpass under the situation of 60 quality % at (methyl) acrylic acid polymer (I-a), the viscosity of the resin combination that obtains becomes too high and has the tendency of operation reduction, or the tendency that exists the surface smoothing generation of the thin slice that obtains to worsen.

When polymerizable monomer (IV) during less than 30 quality %, aqueous softening agent (II) might separate from the cured article of the resin combination that obtains, when polymerizable monomer (IV) surpasses 85 quality %, might take place separating of resin and other compositions.

Then, be that the situation of bridging property polymkeric substance (I-b) describes to polymkeric substance (I).This bridging property polymkeric substance (I-b) is the polymkeric substance with the functional group that can react with linking agent (VI), by carrying out the crosslinked cured article (thermally conductive materials) that forms with the reaction of linking agent (VI).

This bridging property polymkeric substance (I-b) is to make polymerizable monomer (I-b-1) and have the material that polymerizable monomer (I-b-2) copolymerization that is used for crosslinked functional group obtains.Polymerizable monomer (I-b-1) is the polymerizable monomer that has 1 free-radical polymerised unsaturated group at intramolecularly.This monomer (I-b-1) does not have the functional group that can react with linking agent (VI).In addition, polymerizable monomer (I-b-2) is to have 1 at intramolecularly to be used for the crosslinked functional group and the monomer of free-radical polymerised unsaturated group.

As polymerizable monomer (I-b-1), so long as the monomer that has 1 free-radical polymerised unsaturated group at intramolecularly just is not particularly limited.Specifically, with the carbonatoms of the same preferred alkyl of polymerizable monomer (IV) be (methyl) alkyl acrylate of 2～18.The carbonatoms of this alkyl is the usage quantity of (methyl) alkyl acrylate of 2～18, in the monomer component 100 quality % that constitute bridging property polymkeric substance (I-b), be preferably more than the 50 quality %, more preferably more than the 70 quality %, most preferably be more than the 80 quality %.

As the polymerizable monomer that contains functional group (I-b-2), have 1 monomer that is used for crosslinked functional group and free-radical polymerised unsaturated group at intramolecularly and get final product.As functional group, can enumerate carboxyl, hydroxyl, sulfydryl, itrile group, amino, amide group, acid anhydride, epoxy group(ing), isocyanate group.Wherein, preferred hydroxyl.As concrete hydroxyl monomer, for example can enumerate (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) vinylformic acid glyceryl ester, hydroxy styrenes etc.

When polymerizable monomer (I-b-1) and the polymerizable monomer (I-b-2) that contains functional group are carried out polymerization, with respect to both 100 moles of % of total, preferably making the ratio of the polymerizable monomer (I-b-2) that contains functional group is the scope of 0.01～5 mole of %, more preferably 0.1～4 mole of %, most preferably 0.3～3 mole of %.When the polymerizable monomer that contains functional group (I-b-2) surpasses 5 moles of %, the flexibility of the cured article that obtains (thermally conductive materials) reduces sometimes, when less than 0.01 mole of %, aqueous softening agent (II) can't be held in the cured article after crosslinked, is difficult to become gel state sometimes.

The second-order transition temperature of bridging property polymkeric substance (I-b) is preferably below 0 ℃, more preferably-20 ℃ below, more preferably-30 ℃ below.When surpassing 0 ℃, the flexibility of the resin combination that obtains sometimes is insufficient.

For the molecular weight of bridging property polymkeric substance (I-b), preferably use weight-average molecular weight (Mw) based on the polystyrene conversion of GPC in 50,000～2,000,000 scope, more preferably in 80,000～1,500,000 scope, most preferably in 100,000～1,000,000 scope.When Mw less than 50,000 the time, obtaining cured article needs the long period sometimes, or cured article is difficult to become gelatinous resin.On the other hand, when Mw surpassed 2,000,000, the viscosity increased of resin combination was made troubles to operation sometimes.

Bridging property polymkeric substance (I-b) can be by making with the synthetic same method of above-mentioned (methyl) acrylic acid polymer (I-a).Also can in aqueous softening agent (II), synthesize.Bridging property polymkeric substance (I-b) there is no need partially polymerized, and polyreaction is finished.

As linking agent (VI), be used for crosslinked functional group more than 2 and do not have the compound of free-radical polymerised unsaturated group to get final product so long as have at intramolecularly, the functional group that has according to bridging property polymkeric substance (I-b), the kind of functional group that promptly contains the polymerizable monomer (I-b-2) of functional group are suitably selected.For example, as the polymerizable monomer that contains functional group (I-b-2), when being to use monomeric bridging property polymkeric substance (I-b) with hydroxyl, as linking agent (VI), preferably use the compound that in molecule, has 2 above isocyanate group, for example can enumerate 1, hexamethylene-diisocyanate, isophorone diisocyanate, to phenylene diisocyanate, 2, the 6-tolylene diisocyanate, 2,4 toluene diisocyanate, two (4-isocyanic ester cyclohexyl) methane, the TriMethylolPropane(TMP) affixture of tolylene diisocyanate, the isocyanuric acid ester body of tolylene diisocyanate, HDI is an oligopolymer, the isocyanuric acid ester body of HDI or titration body (PVC ユ レ _StarThe ト body) or the isocyanuric acid ester body of urea groups two ketoboidies (ウ レ ト ジ オ Application body), IPDI etc.They can only use a kind, can also be also with more than 2 kinds.In addition, the isocyanate group in the above-mentioned linking agent (VI) can carry out end-blockingization with ε-Ji Neixianan or Diacetylmonoxime or phenol.In addition, as linking agent (VI), (be total to) polymkeric substance that contains isocyanate group that also can use monomer with other monomers (be total to) polymerizations to take place as required and obtain with isocyanate group, but preferable weight-average molecular weight is below 500,000, be for 25 ℃ times aqueous, viscosity be below the 8000mPas about.As monomer, for example can enumerate 2-methacryloyl oxygen base ethyl isocyanate, methacryloyl based isocyanate etc., but be not particularly limited with isocyanate group.The monomer that contains isocyanic ester can only use a kind, can also be also with more than 2 kinds.In addition, the isocyanate group in the monomer also can be by end-blockingization.

Functional group's 1 equivalent that is had with respect to bridging property polymkeric substance (I-b), linking agent (VI) is preferably 0.1 equivalent (more preferably more than 0.5 equivalent, more preferably more than 0.7 equivalent), 2.0 equivalents following (more preferably below 1.8 equivalents, more preferably 1.5 equivalents are following).

The preferred combination that contains the functional group of the functional group of polymerizable monomer (I-b-2) of functional group and linking agent (VI) is, the combination of at least one functional group of from carboxyl, hydroxyl, sulfydryl, amino and amide group, selecting and at least one functional group of from acid anhydride, epoxy group(ing), isocyanate group, selecting.By suitably select to contain the polymerizable monomer (I-b-2) and the linking agent (VI) of functional group, the unreacted functional group that can reduce the cured article that obtains from above-mentioned combination.

Particularly preferred combination is the combination that has the polymerizable monomer that contains functional group of hydroxyl (I-b-2) and have the linking agent (VI) of isocyanate group.By this combination, can be at low temperature more, curing reaction is carried out, the economy excellence.

At polymkeric substance (I) is under the situation of bridging property polymkeric substance (I-b), preferably contains to be useful on crosslinking accelerator, the crosslinked promotion auxiliary agent that promotes crosslinking reaction in resin combination.Particularly when combination has the polymerizable monomer that contains functional group (I-b-2) of hydroxyl and has the linking agent (VI) of isocyanate group, preferably use organometallic compound it to be reacted as crosslinking accelerator.As organometallic compound, have to use and adapt organometallic compound in the periodictable of ordering 3 editions (Japanization association compiles the distribution of the kind Co., Ltd. of ball) records, that belong to the transition metal of 3A～7A, 8,1B family and belong to the metallic element of 2B～6B and get final product, suitably select according to the composition of reaction times, temperature of reaction, resin combination etc. in chemical brief guide.Wherein, the compound of preferred tin, zinc, lead, more preferably tin compound.These organometallic compounds can only use a kind, can also be also with more than 2 kinds.Specifically can enumerate for example organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, two (2 ethyl hexanoic acid) dibutyl tin, oxalic acid dihexyl tin, two lauric acid dioctyl tins, two (iso-octyl mercaptoacetate) dimethyl pink salt, stannous octoate; Organic zinc compounds such as naphthalene acid zinc, 2-ethylhexyl zinc; Organo-lead compounds such as lead stearate, lead naphthenate, 2-ethylhexyl lead etc.

In addition, when crosslinking reaction takes place, preferred and with these crosslinking accelerators with the compound of the atom with lone electron pair is arranged in molecule.Thus, in resin combination, preferably also cooperate this that compound of the atom with lone electron pair is arranged in molecule.This be because, when the promotion experiment of the thermal conductivity thin slice that at high temperature keeps for a long time constituting by such resin cured matter, the inventor etc. find the phenomenon that thin slice hardness reduces, in order to suppress this phenomenon, discovery is when crosslinking reaction, and with above-mentioned organometallic compound with the compound of the atom with lone electron pair is arranged in molecule is effective.Think that it is to be exposed to by the molecular chain because of aqueous softening agent (II) swollen cross-linked polymer that the cross-link bond disengagement causes high temperature play that thin slice hardness reduces, if have the compound that can form the lone electron pair of coordinate bond with atoms metal but exist, though reason is indeterminate, can prevent dissociating of cross-link bond.This hardness reduces the mechanism of preventing and not only the such gelatinous resin that contains the thermal conductivity weighting agent of thermal conductivity thin slice is played a role, and the gelatinous resin that does not contain thermal conductivity weighting agent etc. is played a role too.Thus, when the gelatinous resin with such polyurethane series is applied to the field of use under the high temperature, in order to improve thermotolerance, be preferably under the existence of the compound that has the atom that lone electron pair is arranged in organometallic compound and the molecule, carry out the urethane reaction.

As the compound that has the atom that lone electron pair is arranged in the molecule, preferably in molecule, have the nitrogen-atoms that lone electron pair is arranged or the compound of Sauerstoffatom, particularly preferably in the compound that has the atom of lone electron pair more than 2 is arranged in the molecule.Specifically, can use N, N, N ', N '-tetramethyl--1,6-hexanediamine, N, N, N '-trimethylammonium amino-ethyl carbinolamine, N, N, tertiary amine compounds such as N '-trimethylammonium amino ethyl ethanolamine, hexamethylphosphoramide, or ketone compound such as methyl ethyl diketone.They can also be also with more than 2 kinds.

Usage quantity as the organometallic compound of crosslinking accelerator, with respect to preferred 0.001～3 mass parts of bridging property polymkeric substance (I-b) 100 mass parts, the ratio (mass ratio) that has the compound of the atom that lone electron pair is arranged in organometallic compound and the above-mentioned molecule is preferably 1/1～1/100.

Can in the resin combination that contains bridging property polymkeric substance (I-b), contain acidic cpd.This acidic cpd for example has the homodisperse that can promptly carry out thermal conductivity weighting agent etc. and the effect that improves productivity.In addition, because make the resin combination lowering viscousity, can cooperate a large amount of thermal conductivity weighting agent etc., the heat radiation of the cured article that consequently obtains (thermal conductivity) performance improves.And then, can when making resin combination, remove the air that contains easily.Thus, acidic cpd is brought into play the effect as the necessary thermal conductivity weighting agent of thermally conductive materials to greatest extent.

As acidic cpd, so long as the PKa (acid ionization constant) that compiles II (Japanization association compiles the distribution of the kind Co., Ltd. of ball) definition with chemical brief guide basis is the tart compound more than 1.0, just be not particularly limited, but giving full play on the basis of effect of the present invention, preferred organic system acidic cpd, more preferably carboxylic acid.In addition, acidic cpd is volatilized from cured article, so that the corrosion of electric, the electronic unit that caused by the acidic cpd in the cured article of resin combination etc. do not occur, thereby the boiling point under the further preferred normal pressure is the carboxylic acid below 250 ℃.Such carboxylic acid is that total carbon atom number is 1～8 carboxylic acid.In addition, comprise that in the middle of them substituent can only use a kind, can also be also with more than 2 kinds.

As boiling point is below 250 ℃ and total carbon atom number is 1～8 carboxylic acid, for example can enumerate formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, 2 ethyl hexanoic acid etc.In addition, when solidification value is below 130 ℃ the time, the boiling point of acidic substance under normal pressure that the preferred carboxylic acid that uses is to use is below 170 ℃.

Acidic cpd preferably contains (more preferably more than 0.01 mass parts, more preferably more than 0.03 quality) more than 0.005 mass parts with respect to bridging property polymkeric substance (I-b) 100 mass parts in resin combination.In addition,, preferably contain about 5 mass parts, more preferably contain about 3 mass parts, most preferably contain about 2 mass parts as higher limit.By being set as above-mentioned lower value, higher limit, the fiting effect of acidic cpd can appear.

In the resin combination when polymkeric substance (I) is bridging property polymkeric substance (I-b), when the ratio of aqueous softening agent (II) and bridging property polymkeric substance (I-b) is made as 100 quality % in the total amount with both, preferred aqueous softening agent (II) is 50～90 quality % (more preferably 50～80 quality %, further preferred 55～80 quality %), and preferred bridging property polymkeric substance (I-b) is 10～50 quality % (more preferably 20～50 quality %, further preferred 20～45 quality %).

When aqueous softening agent (II) surpassed 90 quality %, promptly when bridging property polymkeric substance (I-b) during less than 10 quality %, aqueous softening agent is not fully maintenance and do not become gel in cured article sometimes.Consequently, for example exist with the thermal conductivity weighting agent to be squeezed into laminar after mixing and the deterioration of the surface smoothing of thin slice perhaps appears in situation that composition that obtain is clamminess, separating of resin and thermal conductivity weighting agent perhaps occur, so not preferred.On the other hand, when bridging property polymkeric substance (I-b) surpasses 50 quality %, promptly when aqueous softening agent (II) during less than 50 quality %, the viscosity increased of resin combination sometimes, reductions such as operation, the flexibility reduction of the cured article that perhaps obtains.

In resin combination of the present invention, as necessary composition, containing thermal conductivity is the above thermal conductivity weighting agent (III) of 20W/mK.Specifically, for example can enumerate inorganic is weighting agent (oxide compounds such as aluminum oxide, magnesium oxide, zinc oxide, silicon oxide; Oxyhydroxide such as aluminium hydroxide, magnesium hydroxide; Carbide such as silicon carbide; Nitride such as aluminium nitride, boron nitride, silicon nitride), metal is weighting agent [silver, copper, aluminium, iron, zinc, nickel, tin and their alloy (for example copper-tin alloy etc.) etc.], carbonaceous weighting agent (carbon, graphite etc.) etc.In the field that requires the high degree of electrical insulativity, preferably using inorganic is weighting agent.When using them, two or more kinds may be used.For the thermal conductivity of the thermal conductivity weighting agent that uses, can use its sinter and use the thermal conductivity determinator based on hot disk method of capital of a country Electronics Industry Company system: piece number TPA-501 measures.

These thermal conductivitys are the above thermal conductivity weighting agent (III) of 20W/mK, preferably contain 100～1500 mass parts with respect to polymkeric substance (I) 100 mass parts, more preferably contain 200～1300 mass parts.These thermal conductivity weighting agents are many more with respect to the loading level of polymkeric substance (I), and the cured article that obtains (thermally conductive materials) thermal conductivity is high more, and heat dispersion can improve more.But on the other hand, the flexibility of the cured article that obtains has the trend of reduction, so adjust loading level after the flexibility of for example preferred desired thermal conductivity of consideration and cured article.In order to improve the dispersiveness in composition,, as required above-mentioned thermal conductivity weighting agent (III) is carried out surface treatment with silane treatment etc. perhaps in order to increase loading level.In addition, as the shape of above-mentioned thermal conductivity weighting agent (III), can enumerate spherical, fibrous, flakey, plane, broken shape, indefinite shape etc., but be not particularly limited.

In resin combination of the present invention,, can or adhere to resin, inorganic fibre or organic fibre etc. in the surface infiltration of the molding of resin combination for the intensity that improves the cured article that obtains or the property handled etc.In addition, in resin combination of the present invention, only otherwise damage purpose of the present invention, can use known in the past for example reinforcing fiber, inorganic organic filler, polymerization starter, polymerization retarder, low contractionization agent, releasing agent, tackifier, defoamer, thixotropic agent, UV light absorber, ultra-violet stabilizer, oxidation inhibitor, fire retardant, coupler, pigment, dyestuff, magnetic substance, antistatic agent, radio-radar absorber, gelled fuel, paraffin, Microcrystalline Wax, senior fatty oil, thermal softening agent etc. in shaped material field etc. arbitrarily.

As the benchmark of addition, preferably do not damage the amount of the object of the invention degree, particularly, and with respect to polymkeric substance (I) 100 mass parts, the adding up to below 1000 mass parts of preferable additives.The higher limit of preferred addition is 900 mass parts, and preferred higher limit is 800 mass parts.

Resin combination of the present invention is because be aqueous at normal temperatures, so can use known in the past mixing roll.For example can enumerate continuous mixers such as agitator, roll-type stirrer, Banbury agitator, kneading machine, compression type kneading machine, twin shaft mixing roll etc., but be not particularly limited.In addition, can when mixing, remove the air that in composition, contains as required, perhaps when heating or pressurizeing, carry out mixing reducing pressure in installing.In addition, if consider forming operation mixing or that carry out afterwards etc., the viscosity of adding thermal conductivity weighting agent (III) resin combination before preferably is adjusted to below the 5000mPas (more preferably below the 3000mPas, more preferably below the 2200mPas) under 25 ℃.

In addition, in order to prevent the curing of resin combination of the present invention in preservation, preferably separately preserve the constituent of resin combination.When polymkeric substance (I) is above-mentioned (methyl) acrylic acid polymer (I-a), for example preferably is divided into and contains (methyl) acrylic acid polymer (I-a) and polymerizable monomer (IV) and do not contain the 1st raw material of radical polymerization initiator (V) and contain radical polymerization initiator (V) and do not contain the 2nd raw material of above-mentioned polymerizable monomer (IV).Aqueous softening agent (II) is preferably the 1st raw material or the 2nd raw material or suitably divides this both addings.On the other hand, when polymkeric substance (I) is above-mentioned bridging property polymkeric substance (I-b), preferably preserve bridging property polymkeric substance (I-b) and linking agent (VI) respectively.Thus, for example with the mixture of aqueous softening agent (II) and bridging property polymkeric substance (I-b) as the 1st raw material, (VI) gets final product as the 2nd raw material with linking agent.In addition, crosslinking accelerator, compound, acidic cpd that intramolecularly has the atom that lone electron pair is arranged etc. can be engaged in the 1st raw material, the 2nd raw material any or the two in.In any case above-mentioned, when mixing above-mentioned thermal conductivity weighting agent (III), the viscosity increased of mixture is so from the viewpoint of operation, thermal conductivity weighting agent (III) is preferably mixing before being shaped.

By resin combination of the present invention is solidified, can obtain thermally conductive materials.When polymkeric substance (I) is (methyl) acrylic acid polymer (I-a), polymerization by the polymerizable monomer in the composition (IV) is solidified, when polymkeric substance (I) was bridging property polymkeric substance (I-b), making resin combination take place to solidify by the crosslinking reaction with linking agent (VI) became thermally conductive materials.In addition, aqueous softening agent (II) is maintained in the grid of three-dimensional macromolecular chain, so the gel cured article of the softness of obtaining and excellent heat resistance is brought into play good thermal conductivity.Heating temperature during to curing is not particularly limited, but under the situation of polyreaction, be 10 hours high 10～50 ℃ temperature of half life temperature than radical polymerization initiator (V), under the situation of crosslinking reaction, if select to be suitable for the temperature of linking agent, then solidification value is accelerated and can be boosted productivity.

Resin combination of the present invention can be shaped as the shape that needs, and its shape, manufacturing process are not particularly limited.For example, can in mold for injection molding or batch-type mould, drop into above-mentioned resin combination, be configured as the shape that needs, can be configured as laminar by methods such as forcing machine or castings.Laminar member is more useful as the thermal conductivity thin slice.

In addition, Yi Bian,, also can in heating, form Yi Bian carry out resin combination is configured as the operation of the thermally conductive materials that needs shape simultaneously in order to promote polyreaction, crosslinking reaction.And then, in case be configured as the shape that needs, then can heat subsequently or slaking (the long-time preservation under the room temperature), aqueous softening agent (II) is penetrated in the cross-linked polymer and forms gelatinous resin.

In addition, do not use polymkeric substance (I), in the presence of aqueous softening agent (II) and thermal conductivity weighting agent (III), polymerization takes place, can obtain thermally conductive materials of the present invention yet by making the polymerizable monomer (IV) that contains about polyfunctional monomer 0.01～5 quality %.

Make resin combination of the present invention take place to solidify the thermally conductive materials that obtains, preferred hardness is 5～60.This hardness is to use polymer gauge Co., Ltd. system ア ス カ one go system sclerometer C type 25 ℃ of values of measuring down.In addition, only otherwise to add the thermal conductivity weighting agent and make the hardness of the material that its curing obtains in resin combination be 5～80, just can obtain the thermally conductive materials of above-mentioned durometer level.Wherein, Ci Shi hardness is to use polymer gauge Co., Ltd. system ア ス カ one go system sclerometer F type 25 ℃ of values of measuring down.In addition, hardness be meant with scleroscopic probe be expressed to thick 15mm, diameter is the center of the disc shaped test piece about 5～8cm, makes this add pressure surface and adheres on the sample, its 1 second with interior maximum indicator value.

In addition, thermally conductive materials of the present invention preferably demonstrates flexibility steadily in the long term.About whether keeping long-term flexibility, can whether not volatilize by aqueous softening agent (II) and judge, so can be with the rate of mass reduction (%) of maintenance in the time of 168 hours in the baking oven that is heated to 130 ℃ (can be 100 ℃) as target, preferred its rate of mass reduction is below 5%, more preferably below 3%, most preferably be below 2%.

Embodiment

Below, by embodiment the present invention is described in further detail, but following embodiment does not limit the present invention, in the scope that does not break away from the forward and backward aim of stating, change enforcement and all be included in the technical scope of the present invention.Wherein, in embodiment and comparative example, unless otherwise specified, " part " is meant " mass parts ", and " % " is meant " quality % ".

Experiment 1 (relevant polymkeric substance (I) is the experiment of the resin combination of (methyl) acrylic acid polymer (I-a))

Synthesis example 1

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, add 40 parts of 2-EHAs (2EHA), 50 parts of toluene, as 0.3 part of the alpha-methyl styrene of chain-transfer agent, replace gas in the container with nitrogen.Be warming up to 80 ℃, in dropping funnel, add, be added drop-wise in the container with 2 hours times as 0.05 part of the Diisopropyl azodicarboxylate of polymerization starter, the mixed solution of 10 parts of toluene.And then add 0.01 part of Diisopropyl azodicarboxylate, and be warming up to 90 ℃, carry out polymerization in 3 hours.Before polymerization is finished, be blown into air, cooling system and polymerization is finished obtains the mixture of polyacrylic acid 2-ethylhexyl (PEHA) and toluene.Then, to reducing pressure in the system and distilling toluene, obtain PEHA.With regard to the molecular weight that uses this PEHA that GPC (gel permeation chromatography) measures, weight-average molecular weight Mw is 10.6 ten thousand, and number-average molecular weight Mn is 5.1 ten thousand.In addition, the second-order transition temperature that uses differential scanning calorimetry and adopt ordinary method to measure is-60 ℃.

Synthesis example 2

In the container that possesses thermometer, agitator, gas introduction tube and reflux exchanger, add lauryl methacrylate(LMA) (LMA) 100 parts, replace gas in the container with nitrogen.Be warming up to 80 ℃, add, under nitrogen atmosphere, carry out 3.0 hours mass polymerization as 0.2 part of the thiohydracrylic acid of chain-transfer agent with as 0.01 part of the Diisopropyl azodicarboxylate of polymerization starter.Before polymerization is finished, be blown into air and add 0.1 part of polymerization retarder quinhydrones simultaneously, then cooling system and make to be aggregated in midway and finish.Polylauryl methacrylate in the mixture that obtains (PLMA) is 50.0%, is 50.0% as the LMA of polymerizable monomer (IV) composition.The viscosity of the PLMA that obtains under 25 ℃ is 4980mPas.With regard to the molecular weight of the PLMA that measures by GPC, weight-average molecular weight Mw=13.6 ten thousand, and number-average molecular weight Mn=5.8 ten thousand, and the second-order transition temperature that uses differential scanning calorimetry also to adopt ordinary method to measure is-65 ℃.

No.1-1

By 30 parts of PEHA, as 39 parts of monomeric LMA, 1 part of (chemistry society of common prosperity company system of polydimethyl vinylformic acid glycol ester as polyfunctional monomer, trade(brand)name " ラ イ ト エ ス テ Le 9EG "), 30 parts of (Asahi Electro-Chemical Co. Ltd's systems of aqueous softening agent of trimellitate system, trade(brand)name " ア デ カ サ イ ザ one C880 ") mixture of Gou Chenging (below, sometimes the mixture that adds before the polymerization starter is become " aqueous resin ") in 100 parts, add 1 part of peroxidation 1 as thermal polymerization, 1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate (chemical drug ア Network ゾ corporate system; Trade(brand)name " カ ヤ エ ス テ Le TMPO-70 ") carries out deaeration, the material that obtains is injected into thickness to be configured to having of 15mm and to implement in the glass guide channel of the PET film that the demoulding handles, polymerization is 1 hour in 80 ℃ baking oven, and then 100 ℃ of following polymerizations 1 hour, obtains tabular cured article.Under following benchmark, the cured article that obtains is carried out measurement of hardness, the results are shown in table 2.In addition, aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one the C880 ") 3g that uses is put in the aluminum watch-glass of diameter as 5cm, the rate of mass reduction when the baking oven that is heated to 130 ℃ keeps 24 hours is 0.07%.In addition, the viscosity under 25 ℃ is 100mPas, and zero pour is-21 ℃.

Then, with 100 parts of above-mentioned aqueous resins, as above-mentioned " カ ヤ エ ス テ Le TMPO-70 " 1 part, 0.1 part of (PVC of defoamer of thermal polymerization _StarNetwork ケ ミ one corporate system, trade(brand)name " A-515 "), thermal conductivity is 400 parts of (clear and electrician's corporate systems of aluminum oxide of 30W/mK; Piece number AS-10) carries out evenly mixingly, obtain the thermally conductive materials resin combination.Subsequently, resin combination is carried out deaeration, be injected into thickness and be configured to having of 1mm and implement in the glass guide channel of the PET film that the demoulding handles, polymerization is 1 hour in being set as 80 ℃ baking oven, and then 100 ℃ of following polymerizations 1 hour, makes its curing.With following benchmark the characteristic of the sheet cured article that obtains is estimated, be the results are shown in table 2.

[hardness of tabular cured article]

As mentioned above, with respect to 100 parts of aqueous resins, interpolation is as above-mentioned " カ ヤ エ ス テ Le TMPO-70 " 1 part and mixing, the deaeration of thermal polymerization, then this mixture is injected in the container that thickness is configured to 15mm, heating is 1 hour in 80 ℃ baking oven, and then under 100 ℃, heated 1 hour, make this mixture solidified.The ア ス カ one go system F type hardness tester meter of polymer gauge Co., Ltd. system is placed into the center of measuring sample, scleroscopic probe is expressed to is cut into thick 15mm, diameter is the center of the disc shaped test piece about 5～8cm, make this add the pressure surface adherence on sample, be used as hardness with interior maximum indicator value its 1 second.Mensuration is carried out under 25 ℃.

[plasticity of thin slice]

The surface of the laminar cured article that visual observation obtains in above-mentioned is estimated with following benchmark.

Zero: do not have uneven or bubble exists at slice surfaces, do not have yet resin and inorganic filler separate and evenly, superficiality is good.

*: have uneven or the bubble existence at slice surfaces, separating of resin and inorganic filler perhaps occur, obtain uneven thin slice.

[the initial stage thermal conductivity of thin slice]

Adopt the rapid thermal conductivity of the capital of a country electronic industry system number of reckoning by the piece QTM-500 to measure.Working sample uses laminar cured article is stacked and make the thin slice of its thickness as 10mm.Mensuration is carried out under 25 ℃.

[the initial stage hardness of thin slice]

With JIS K7312 is benchmark, uses the ア ス カ one go system sclerometer C type of polymer gauge Co., Ltd. system to measure.Working sample uses and carries out laminar cured article stacked and make the thin slice of its thickness as 10mm, and is identical with the situation of above-mentioned F type, measures under 25 ℃.The more little flexibility that is imbued with more of the numerical value that obtains.

[thermotolerance]

Laminar cured article was kept 168 hours in being set as 130 ℃ baking oven, then quality measurement decrement, hardness, thermal conductivity.Rate of mass reduction is by (weight before measuring-mensuration back weight)/weight * 100=rate of mass reduction (%) is obtained before measuring.Hardness, thermal conductivity with initial stage hardness, the initial stage thermal conductivity is the same measures.Difference of hardness before the thermal test after (the initial stage hardness of thin slice) and the test is more little, has secular flexibility more.

[weather resistance]

Obtain the initial stage hardness of thin slice and the difference of hardness (△ hardness) of the thin slice hardness behind the thermal test.If its value is less, the flexibility of thin slice can keep for a long time, so when making this thin slice between Heating element and heat conductor, can keep contact area for a long time with them, consequently do not reduce, can have long-time and stable thermal conduction characteristic from the heat transfer efficiency of Heating element to heat conductor.

No.1-2

Make by 30 parts of PEHA, the aqueous resin that constitutes as 59 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 10 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1 the results are shown in table 2.

No.1-3

Make by 30 parts of PEHA, the aqueous resin that constitutes as 64 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 5 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-4

Make by 30 parts of PEHA, the aqueous resin that constitutes as 29 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 40 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-5

Make by 15 parts of PEHA, the aqueous resin that constitutes as 34 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 50 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-6

Make by 30 parts of PEHA, the aqueous resin that constitutes as 29 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 30 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-7

Make by 30 parts of PEHA, the aqueous resin that constitutes as 39 parts of monomeric 2-EHAs, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 30 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-8

Make by 30 parts of PEHA, the aqueous resin that constitutes as 39 parts of monomeric n-butyl acrylates, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 30 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-9

Make by 30 parts of PEHA, as 39 parts of monomeric 2EHA, as 30 parts of (Asahi Electro-Chemical Co. Ltd's systems of aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system; Trade(brand)name " ア デ カ サ イ ザ one C79 ") the aqueous resin of Gou Chenging is in addition the same with No.1-1, obtains tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.In addition, aqueous softening agent (Asahi Electro-Chemical Co. Ltd's system, trade(brand)name " ア デ カ サ イ ザ one the C79 ") 3g that uses is put in the aluminum watch-glass that diameter is 5cm, the rate of mass reduction when the baking oven that is heated to form 130 ℃ keeps 24 hours is 0.09%.In addition, the viscosity under 25 ℃ is 100mPas, and zero pour is-22 ℃.

No.1-10

Make by 70 parts in the mixture that in synthesis example 2, obtains, be PLMA35 part, the aqueous resin that constitutes as 35 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 29 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-11

Make by 70 parts in the mixture that in synthesis example 2, obtains, be 35 parts of PLMA, the aqueous resin that constitutes as 35 parts of monomeric LMA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 29 parts (above-mentioned " ア デ カ サ イ ザ one C79 "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.

No.1-12

Make by 30 parts of PEHA, as 39 parts of monomeric 2EHA, as 30 parts of (aginomoto Off ア イ テ Network ノ corporate systems of aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), phosphoric acid ester system; Trade(brand)name " Network ロ ニ テ _StarNetwork ス TXP ") the aqueous resin that constitutes, in addition the same with No.1-1, obtain tabular cured article, thermally conductive materials with resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.In addition, with aqueous softening agent (the aginomoto Off ア イ テ Network ノ corporate system of using; Trade(brand)name " Network ロ ニ テ _StarNetwork ス TXP ") 3g puts in the aluminum watch-glass that diameter is 5cm, is 0.20% at the rate of mass reduction of baking oven maintenance in the time of 24 hours that is heated to form 130 ℃.In addition, the viscosity under 25 ℃ is 175mPas, and zero pour is-15 ℃.

No.1-13 (relatively using)

Make (promptly by the aqueous resin that constitutes as 69 parts of monomeric 2EHA, as the aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), trimellitate system 30 parts (above-mentioned " ア デ カ サ イ ザ one C880 "), do not contain (methyl) acrylic acid polymer) as necessary composition, in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.In addition, estimate the same with No.1-1, evaluation result is shown in table 2.Separating of the laminar cured article generation resin that obtains and the aluminum oxide of weighting agent, obtain uneven thin slice.For this reason, do not carry out its later evaluation.

No.1-14 (relatively using)

Make by the aqueous resin that constitutes as 99 parts of monomeric 2EHA, as the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG ") (promptly do not contain as must composition (methyl) acrylic acid polymer, aqueous softening agent), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.The hardness value of the tabular cured article that obtains is 78, and is all bigger than any tabular cured article that obtains in example of the present invention.Separating of the thin slice generation resin that obtains and the aluminum oxide of weighting agent, obtain uneven thin slice.For this reason, do not carry out its later evaluation.

No.1-15 (relatively using)

Make by 30 parts of PEHA, the aqueous resin (promptly do not contain as must composition aqueous softening agent) that constitutes as 69 parts of monomeric 2EHA, as the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), in addition, the same with No.1-1, obtain tabular cured article, thermally conductive materials resin combination and sheet cured article thereof.Estimate the same with No.1-1, evaluation result is shown in table 2.The hardness value of the tabular cured article that obtains is 71, and the hardness value of thin slice initial stage hardness is 80, and is all bigger than any tabular cured article that obtains in example of the present invention.For this reason, for example ought make it between for example Heating element such as PDP, electrical and electronic parts with for example between the heat conductors such as heat sink, thermal conductivity radiator element, metal sheet, when heat conduction is carried out in the heating of PDP, electrical and electronic parts etc., reduce with their contact area, thermal conduction characteristic might reduce.In addition, the thin slice hardness behind the thermal test is 98, and the hardness change before and after the test is all bigger than any cured article that obtains in example of the present invention.For this reason as can be known, do not have secular flexibility, stable thermal conduction characteristic generation deterioration yet.

Wherein, as follows at the abbreviation shown in the table 2.

PEHA: the polyacrylic acid 2-ethylhexyl that in synthesis example 1, obtains

PLMA: the polylauryl methacrylate that in synthesis example 2, obtains

2EHA: 2-EHA

LMA: lauryl methacrylate(LMA)

BA: n-butyl acrylate

9EG: chemistry society of polydimethyl vinylformic acid glycol ester common prosperity company system; Trade(brand)name " ラ イ ト エ ス テ Le 9EG "

C880: the aqueous softening agent of Asahi Electro-Chemical Co. Ltd's system; Trade(brand)name " ア デ カ サ イ ザ one C880 "

C79: the aqueous softening agent of Asahi Electro-Chemical Co. Ltd's system; Trade(brand)name " ア デ カ サ イ ザ one C79 "

TMPO70: chemical drug ア Network ゾ corporate system thermal polymerization; Trade(brand)name: " カ ヤ エ ス テ Le TMPO70 "

A-515: PVC _StarNetwork ケ ミ one corporate system defoamer; Trade(brand)name " A-515 "

△ hardness: the difference of hardness of the thin slice hardness value behind thin slice initial stage hardness value and the thermal test

No.1-16

Use the compression type kneader, will be by 70 parts in the mixture that in synthesis example 2, obtains, be PLMA35 part, as 35 parts of monomeric LMA, as 29 parts of (KAO. Corp. SA's systems of aqueous softening agent of the polydimethyl vinylformic acid glycol ester of polyfunctional monomer 1 part (above-mentioned " ラ イ ト エ ス テ Le 9EG "), terephthalate system, trade(brand)name " PVC ニ サ イ ザ 1 ") the aqueous resin of Gou Chenging, with 10 hours half life temperatures as thermal polymerization be 95 ℃ tert-pentyl peroxide 3,5,2 parts of (chemical drug ア Network ゾ corporate systems of 5-tri-methyl hexanoic acid ester; Trade(brand)name " カ ヤ エ ス テ Le AN "), thermal conductivity is 1300 parts of (clear and electrician's corporate systems of aluminum oxide of 30W/mK; Piece number AS-40) carry out mixing.And, aqueous softening agent (above-mentioned " PVC ニ サ イ the ザ 1 ") 3g that uses to be put in the aluminum watch-glass of diameter as 5cm, the rate of mass reduction when the baking oven that is heated to form 130 ℃ keeps 24 hours is 0.43%.In addition, the viscosity under 25 ℃ is 65mPas, and zero pour is-22 ℃.

Subsequently, use extrusion machine, extruding and set its thickness between 2 PET films is 1mm, obtains flap.Obtain that resin does not separate with inorganic filler and thin slice uniformly.In addition, do not have bubble, do not have surface irregularity yet on the surface.Thus, plasticity is good.

The thermal conductivity of this sheet cured article is 3.3W/mK, shows excellent thermal conductivity.In addition, flexibility (hardness) is measured, the result is 49.Hardness is to use the system ア ス カ of polymer gauge Co., Ltd. one go system sclerometer A type, 25 ℃ of duroscope hardness tests (type A test) of implementing JIS K6253 record down, measures thus.

Experiment 2 (relevant experiment of in aqueous softening agent, synthesizing the resin combination of (methyl) acrylic acid polymer (I-a))

Production Example 1～5

In the Glass Containers that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, add the 1st (methyl) acrylic polymerizable monomer [and the 2nd (methyl) acrylic polymerizable monomer as required], the 1st aqueous softening agent, chain-transfer agent, replace with nitrogen, the oxygen concn that makes the gas phase part in the reaction vessel is 0.1 quality % following (the adding stage).Be warming up to specified temperature (A), as required the polymerization starter (reaction initial stage) that drips at the appointed time and diluted with aqueous softening agent from dropping funnel with dilution.Then, under specified temperature (B), continue to stir (reaction sustained period) with the specified time.Further append polymerization starter as required, under specified temperature (C), continue to stir (reaction maturation stage) with the specified time.Be blown into air, and cooling, polymerization is finished, obtain containing mixture 2-A～2-E of polymkeric substance 2-A～2-E etc.Wherein, in any example, all there be not the out of control of polyreaction.Detailed content is shown in following table 3.In Production Example 5, using polyether ester is aqueous softening agent (Asahi Electro-Chemical Co. Ltd's system; Trade(brand)name " ア デ カ サ イ ザ one S700 "), but the rate of mass reduction of this aqueous softening agent big (2.95%), outside the present invention.

In table 3,, obtain by calculate remaining the 1st (methyl) acrylic polymerizable amount of monomer by vapor-phase chromatography (GC) about percent polymerization.

Modulation example 1～5

With the mixed said mixture 2-A～2-E shown in the following table 4 and various other materials, modulate (methyl) acrylic acid series liquid resin composition 2-A～2-E shown in the following table 4.Containing the monomeric material of (methyl) acrylic polymerizable in fact, is solidified material by radical polymerization (thermopolymerization), so be called " polymerizability ".

No.2-1

To metha crylic polymerizability liquid resin composition 2-A 100 mass parts, as tert-pentyl peroxide-2-ethylhexanoate (chemical drug ア Network ゾ Co., Ltd. system, trade(brand)name " the ト リ go ノ of radical polymerization initiator _StarNetwork ス 121-50E ") 1 mass parts, defoamer (above-mentioned " A-515 ") 0.1 mass parts, aluminum oxide (above-mentioned AS-10; Thermal conductivity is 30W/mK) 400 mass parts carry out evenly mixing after, deaeration.Apply in the glass guide channel on the bottom implementing PET film that the demoulding handles, injecting above-mentioned deaeration thing and making thickness is 1mm, is 100 ℃ baking oven internal heating 1 hour in temperature, then in the heating 1 hour down of 120 ℃ of temperature, makes its polymerization (curing).

No.2-1～2-5

Use acrylic polymerizable liquid resin composition 2-B～2-E to replace metha crylic polymerizability liquid resin composition 2-A, in addition, identical with No.2-1.

The same sheet cured article that in No.2-1～2-5, obtains of estimating during with above-mentioned experiment 1.In addition, with regard to heat-resisting decomposability, be to continue the sheet cured article is heated at 130 ℃, make to reach 336 hours heat-up time and 504 hours, with the above-mentioned result who similarly observes hardness.

Polymerizability liquid resin composition 2-A～2-D is keeping the usage quantity (with reference to table 4) that the low viscous while can suppress aqueous softening agent.In addition, 2-A compares with the metha crylic liquid resin composition, and acrylic acid series liquid resin composition 2-B～2-D can reach further lowering viscousity (with reference to table 4).In addition, liquid resin composition 2-A～2-D can substantially make under the situation without special catalyst, solvent and make.Particularly substantially do not use under the situation of special catalyst, solvent and can make acrylic acid series liquid resin composition 2-B～2-D, merit attention in this point.

And the cured article from polymerizability liquid resin composition 2-A～2-D obtains even at high temperature add the time of thermoae length, does not produce and oozes out, heat-resisting decomposability excellence (with reference to table 5).But in the No.2-5 of material as aqueous softening agent of the polyether ester system that uses the thermotolerance deterioration, the rate of mass reduction after the heating is big, thermotolerance deterioration (with reference to table 5).

Experiment 3 (relevant polymkeric substance (I) is the experiment of the resin combination of bridging property polymkeric substance (I-b))

Synthesis example 3

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, put into 39.48 parts of 2EHA, vinylformic acid 2-hydroxyl ethyl ester (HEA) 0.52 part (the hydroxyl monomer of total polymerization monomer is set as 2 moles of %), be 50 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 "), replace gas in the container with nitrogen as the trimellitate of aqueous softening agent.Be warming up to 75 ℃, in dropping funnel, add dimethyl-2 as polymerization starter, 0.05 part of 2-azo two (2 Methylpropionic acid ester) and trimellitate were the mixture of 10 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 "), with 3 hours times dropping.And then adding dimethyl-2 as polymerization starter, two (the 2 Methylpropionic acid esters) 0.02 part of 2-azo are warming up to 90 ℃, carry out polymerization in 3 hours.Before finishing, polymerization adds as 0.4 part of the dibutyl tin laurate of crosslinking accelerator, be blown into air, cooling system and polymerization is finished, obtain the mixture that acrylic copolymer that contains 2 moles of % hydroxyls and trimellitate as the bridging property polymkeric substance be aqueous softening agent (below, be called acrylic resin 3-A).The residual 2EHA that obtains by vapor-phase chromatography (GC) is 0.1%, and the acrylic copolymer that contains 2 moles of % hydroxyls as the bridging property polymkeric substance among the acrylic resin 3-A is 39.9%.

Viscosity under 25 ℃ of the acrylic resin 3-A that obtains is 12980mPas.With regard to the molecular weight of the polymkeric substance that used GPC, weight-average molecular weight Mw is 110.6 ten thousand, and number-average molecular weight Mn is 10.1 ten thousand.In addition, the second-order transition temperature as the acrylic copolymer that contains 2 moles of % hydroxyls of bridging property polymkeric substance that uses differential scanning calorimetry and adopt that ordinary method measures is-64 ℃.

Synthesis example 4

In reaction vessel, add 39.70 parts of 2EHA, HEA 0.30 part (the hydroxyl monomer in the total polymerization monomer is set as 1 mole of %), be 50 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") as the trimellitate of aqueous softening agent, in addition, the same with synthesis example 3, obtain the mixture that acrylic copolymer that contains 1 mole of % hydroxyl and trimellitate as the bridging property polymkeric substance be aqueous softening agent (below, be called acrylic resin 3-B).

Residual 2EHA by GC is 0.1%, and the acrylic copolymer that contains 1 mole of % hydroxyl as the bridging property polymkeric substance among the acrylic resin 3-B is 39.9%.Viscosity under 25 ℃ of the acrylic resin 3-B that obtains is 11500mPas.With regard to the molecular weight of the polymkeric substance that used GPC, weight-average molecular weight Mw is 100.6 ten thousand, and number-average molecular weight Mn is 10.5 ten thousand.In addition, the second-order transition temperature as the acrylic copolymer that contains 1 mole of % hydroxyl of bridging property polymkeric substance that uses differential scanning calorimetry and adopt that ordinary method measures is-62 ℃.

Synthesis example 5

Except being aqueous softening agent is altered to above-mentioned " ア デ カ サ イ ザ one C79 " with trimellitate, the same with synthesis example 3, obtain the mixture that acrylic copolymer that contains 2 moles of % hydroxyls and trimellitate as the bridging property polymkeric substance be aqueous softening agent (below, be called acrylic resin 3-C).The residual 2EHA that obtains by GC is 0.1%, and the acrylic copolymer that contains 2 moles of % hydroxyls as the bridging property polymkeric substance among the acrylic resin 3-C is 39.9%.Viscosity under 25 ℃ of the acrylic resin 3-C that obtains is 11500mPas.With regard to the molecular weight of the polymkeric substance that used GPC, weight-average molecular weight Mw is 110.6 ten thousand, and number-average molecular weight Mn is 13.5 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the acrylic copolymer that contains 2 moles of % hydroxyls that ordinary method measures to be-65 ℃.

No.3-1

By 62 parts of acrylic resin 3-A, trimellitate is that the aqueous resin of 38 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") (is made the acrylic copolymer that contains 2 moles of % hydroxyls about 25% that contains as the bridging property polymkeric substance for 100 parts, the aqueous resin that contains aqueous softening agent about 75%) in, add 0.1 part of defoamer (above-mentioned " A-515 "), as 0.86 part of the isophorone diisocyanate of linking agent (be with aqueous resin in the suitable amount of isocyanate of hydroxyl molar weight of acrylic copolymer), carry out deaeration, the material that obtains is injected into thickness to be set to having of 15mm and to implement in the glass guide channel of the PET film that the demoulding handles, heating is 2 hours in 80 ℃ baking oven, make aqueous resin gelization, obtain tabular cured article.

Then, to 100 parts of above-mentioned aqueous resins, defoamer 0.1 part (above-mentioned " A-515 "), carry out mixingly uniformly as 0.86 part of the isophorone diisocyanate of linking agent, aluminum oxide that thermal conductivity is 30W/mK 200 parts (above-mentioned AS-10), obtain the thermally conductive materials resin combination.Subsequently, this thermally conductive materials is carried out deaeration with resin combination, being injected into thickness is configured to having of 1mm and implements in the glass guide channel of the PET film that the demoulding handles, heated 2 hours down at 80 ℃, the hydroxyl in the said composition and the reaction of isocyanate group are finished, obtain the sheet cured article of thermally conductive materials with resin combination.About above-mentioned tabular cured article and sheet cured article, with the experiment 1 the same characteristic of estimating, the result is as shown in table 6.Wherein, stable on heating evaluation was carried out under 100 ℃ * 168 hours.

No.3-2

Use is by 75 parts of acrylic resin 3-A, trimellitate is that the aqueous resin of 25 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") (is made the acrylic copolymer that contains 2 moles of % hydroxyls about 30% that contains as the bridging property polymkeric substance for 100 parts, the aqueous resin that contains aqueous softening agent about 70%), as 1.03 parts of the isophorone diisocyanates of linking agent (be with aqueous resin in the suitable amount of isocyanate of hydroxyl molar weight of acrylic copolymer), in addition, the same tabular cured article that obtains aqueous resin with No.3-1, and the thermally conductive materials sheet cured article of resin combination.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-3

Use is 100 parts of the aqueous resins (make and contain aqueous resin about 25% as the acrylic copolymer that contains 1 mole of % hydroxyl of bridging property polymkeric substance, that contain aqueous softening agent about 75%) of 38 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") by 62 parts of acrylic resin 3-B, trimellitate, as 0.43 part of the isophorone diisocyanate of linking agent, in addition, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-4

Use is 100 parts of the aqueous resins (make and contain aqueous resin about 30% as the acrylic copolymer that contains 1 mole of % hydroxyl of bridging property polymkeric substance, that contain aqueous softening agent about 70%) of 25 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") by 75 parts of acrylic resin 3-B, trimellitate, as 0.52 part of the isophorone diisocyanate of linking agent, in addition, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-5

Use is 100 parts of the aqueous resins (make and contain aqueous resin about 25% as the acrylic copolymer that contains 2 moles of % hydroxyls of bridging property polymkeric substance, that contain aqueous softening agent about 75%) of 38 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C79 ") by 62 parts of acrylic resin 3-C, trimellitate, in addition, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-6

Use is 100 parts of the aqueous resins (make and contain aqueous resin about 30% as the acrylic copolymer that contains 2 moles of % hydroxyls of bridging property polymkeric substance, that contain aqueous softening agent about 70%) of 25 parts of formations of aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C79 ") by 75 parts of acrylic resin 3-C, trimellitate, in addition, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-7

Except aluminum oxide being made into 100 parts of (upright altogether マ テ リ ア Le corporate systems of boron nitride that thermal conductivity is 50W/mK; Piece number BN-100) outside, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-8

Except aluminum oxide being made into 200 parts of (Japan's aluminium corporate systems of aluminium nitride that thermal conductivity is 120W/mK; Piece number R-15) outside, the same tabular cured article of aqueous resin and the sheet cured article that thermally conductive materials is used resin combination of obtaining with No.3-1.In addition, estimate the same with No.3-1 the results are shown in table 6.

No.3-9 (relatively using)

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, add 39.70 parts of 2EHA, HEA 0.30 part of (the hydroxyl monomer in the total monomer is set as 1 mole of %), 50 parts of toluene, as 0.2 part of the alpha-methyl styrene of chain-transfer agent, replace gas in the container with nitrogen.Be warming up to 80 ℃, in dropping funnel, add, with 2 hours times dropping as 0.05 part of the Diisopropyl azodicarboxylate of polymerization starter, the mixture of 10 parts of toluene.And then add 0.01 part of Diisopropyl azodicarboxylate, and be warming up to 90 ℃, carry out polymerization in 3 hours.Before polymerization is finished, add as 0.4 part of the dibutyl tin laurate of crosslinking accelerator, be blown into air, cooling system and polymerization is finished obtains containing the toluene resin solution as the multipolymer that contains 1 mole of % hydroxyl 40% of bridging property polymkeric substance.With regard to the molecular weight of the multipolymer that uses GPC, weight-average molecular weight Mw is 30.6 ten thousand, and number-average molecular weight Mn is 10.1 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the multipolymer that ordinary method measures to be-60 ℃.

Then, in 100 parts of the above-mentioned toluene resin solution of the aqueous softening agent of necessary composition that does not contain aqueous resinous principle, interpolation as 0.69 part of the isophorone diisocyanate of linking agent (be with toluene resin solution in the suitable amount of isocyanate of amount of hydroxyl groups of bridging property polymkeric substance), the material that obtains is launched on the PET film of implementing demoulding processing, and to make thickness be 15mm, and then distill toluene fully to reducing pressure in the system.Then heating 2 hours in 80 ℃ baking oven reacts hydroxyl in the polymkeric substance and isocyanic ester and obtains gelling material.The same gelling material that obtains of estimating with No.3-1, the result is as shown in table 6.

Then, with 100 parts of above-mentioned toluene resin solution, as 80 parts in 0.69 part of isophorone diisocyanate, the aluminum oxide (above-mentioned AS-10) of linking agent (with respect to 100 parts in the bridging property polymkeric substance in the toluene resin solution, addition is 200 parts) evenly mixing, obtain the thermally conductive materials resin combination.Subsequently, implementing to launch this thermally conductive materials resin combination on the PET film that the demoulding handles, and to make its thickness be 1mm, the system inner pressure relief is distilled toluene fully.Then in 80 ℃ baking oven, heated 2 hours, hydroxyl and isocyanic ester in the polymkeric substance are reacted, obtain the cured article of flaky thermally conductive materials with resin combination.The same thin slice that obtains at this moment of estimating with No.3-1.Evaluation result is as shown in table 6.

The hardness value of the gel that obtains in the No.3-9 of usefulness relatively is 95.This is not to keep aqueous softening agent and the gel that obtains in cross-linked polymer, so the hardness height of this gel becomes the result of flexibility deterioration.In addition, thin slice initial stage hardness is 70, and is all bigger than any cured article that obtains in example of the present invention.For this reason, when making it between for example Heating element such as PDP, electrical and electronic parts, and for example between the heat conductors such as heat sink, radiator element, metal sheet, when the heating of PDP, electrical and electronic parts etc. is dispelled the heat, reduce with their contact area, heat dissipation characteristics might reduce.In addition, the result who carries out thermal test is that rate of mass reduction is 0.6%, and thin slice hardness is 89, and the hardness change before and after the test is all bigger than any cured article that obtains in example of the present invention.For this reason as can be known, also do not have secular flexibility, stable heat dissipation characteristics is poor.

No.3-10 (relatively using)

Distill toluene fully from the toluene resin solution that relatively with No.3-9, obtains, obtain the multipolymer that contains 1 mole of % hydroxyl as the bridging property polymkeric substance.

By above-mentioned as 75 parts of the multipolymers that contains 1 mole of % hydroxyl of bridging property polymkeric substance, as the normal temperature of thermal softening agent under for solid shape and fusing point be 25 parts of (Japanese smart wax corporate systems of paraffin of 47 ℃; Piece number solid paraffin 115) in the heat-softened resin of Gou Chenging 100 parts (promptly not containing aqueous softening agent) as the necessary composition of aqueous resin, interpolation as 1.30 parts of the isophorone diisocyanates of linking agent (be with heat-softened resin in the suitable amount of amount of hydroxyl groups of bridging property polymkeric substance), the material that obtains is handled on the PET film and launched implementing the demoulding, and thickness setting become 15mm, heating is 2 hours in 80 ℃ baking oven, hydroxyl in the polymkeric substance and isocyanic ester is reacted obtain gelling material.The same gelling material that obtains of estimating with No.3-1, the result is as shown in table 6.

Then, use the compression type kneader, under 50 ℃ with 100 parts of above-mentioned heat-softened resins, as mixing 30 minutes of 1.30 parts of the isophorone diisocyanates of linking agent, aluminum oxide that thermal conductivity is 30W/mK 200 parts (above-mentioned AS-10).Subsequently, use extrusion machine to be expressed between 2 the PET film and and be set as 1mm, obtain flaky thermally conductive materials resin combination thickness.Then, with resin combination heating 2 hours, the hydroxyl in the composition and the reaction of isocyanate group are finished at 80 ℃ of flaky thermally conductive materials that will obtain down.The same thin slice that obtains at this moment of estimating with No.3-1.Evaluation result is as shown in table 6.

The hardness value of the gel that obtains is 90.This is not to keep aqueous softening agent and the gel that obtains in cross-linked polymer, so the hardness height of this gel becomes the result of flexibility deterioration.In addition, thin slice initial stage hardness is 60, and is all bigger than any cured article that obtains in example of the present invention.For this reason, when making it between for example Heating element such as PDP, electrical and electronic parts, and for example between the heat conductors such as heat sink, radiator element, metal sheet, when the heating of PDP, electrical and electronic parts etc. is dispelled the heat, reduce with their contact area, heat dissipation characteristics might reduce.

In addition, the thin slice that obtains is relatively uneven with the separating of inorganic filler of resin and use, but exists uneven or bubble on the surface, the surface smoothing deterioration.The plasticity that is thin slice is bad.

In addition, carry out thermal test the result be that rate of mass reduction is 6.1%, the maximum value of thin slice hardness surpasses 100.Think that this is because of the volatilization because of employed thermal softening agent rate of mass reduction to be increased, changes in hardness also increases.Therefore, the thin slice that obtains does not have secular flexibility, and stable heat dissipation characteristics is poor.And then many places expand on the thin slice after the oven test.

In addition, the symbol that uses in table 6 is as follows.

C880: Asahi Electro-Chemical Co. Ltd's system, aqueous softening agent: trade(brand)name " ア デ カ サ イ ザ one C880 "

C79: Asahi Electro-Chemical Co. Ltd's system, aqueous softening agent: trade(brand)name " ア デ カ サ イ ザ one C79 "

Linking agent: isophorone diisocyanate

A-515: PVC _StarNetwork ケ ミ one corporate system, defoamer; Trade(brand)name " A-515 "

△ hardness: the difference of hardness of the thin slice hardness value behind thin slice initial stage hardness value and the thermal test

Experiment 4 (experiment of the resin combination when relevant polymkeric substance (I) is bridging property polymkeric substance (I-b))

No.4-1

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, adding 39.7 parts of 2EHA, HEA 0.3 part of (the hydroxyl monomer in the total polymerization monomer is set as 1 mole of %), phthalic ester is 50 parts in aqueous softening agent (above-mentioned " PVC ニ サ イ ザ 1 "), replaces gas in the container with nitrogen.Be warming up to 80 ℃, adding 0.05 part of the Diisopropyl azodicarboxylate and the above-mentioned phthalic ester that have mixed as polymerization starter in dropping funnel was the material of 10 parts in aqueous softening agent (above-mentioned " PVC ニ サ イ ザ 1 "), with 2 hours times dropping.And then add 0.02 part of Diisopropyl azodicarboxylate, and be warming up to 90 ℃, carry out polymerization in 3 hours.Before finishing, polymerization further adds 60 parts in above-mentioned aqueous softening agent, be blown into air, cooling system and polymerization is finished obtains containing the acrylic copolymer of 1 mole of % hydroxyl and the mixture that phthalic ester is aqueous softening agent (below, be called acrylic resin No.4-1).The residual 2EHA that obtains by vapor-phase chromatography (GC) is 0.1%, and the acrylic copolymer that contains 1 mole of % hydroxyl among the acrylic resin No.4-1 is 24.8%.

Viscosity under 25 ℃ of the acrylic resin No.4-1 that obtains is 1980mPas.With regard to the molecular weight of the polymkeric substance that used GPC, weight-average molecular weight Mw is 50.6 ten thousand, and number-average molecular weight Mn is 20.1 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the acrylic copolymer that contains 1 mole of % hydroxyl that ordinary method measures to be-64 ℃.

Then, use the compression type kneader, under 25 ℃, with 100 parts of acrylic resin No.4-1, as the isophorone diisocyanate of linking agent 0.26 part (amount of isocyanate that is equivalent to the hydroxyl molar weight among the acrylic resin No.4-1), as mixing 30 minutes of 0.1 part of the dibutyl tin laurate of crosslinking accelerator, aluminum oxide that thermal conductivity is 30W/mK 1300 parts (above-mentioned AS-10).Subsequently, use extrusion machine to be expressed between 2 the PET film and and be set as 1mm, obtain flaky thermally conductive materials resin combination thickness.Then, at room temperature place the flaky thermally conductive materials obtain with resin combination 24 hours, the hydroxyl in the composition and the reaction of isocyanate group are finished.The thermally conductive materials that obtain this moment is not clamminess with thin slice (thermal conductivity thin slice), and the phthalic ester of use is that aqueous softening agent is held in cross-linked polymer, becomes gelatinous resin.In addition, do not separate, relatively evenly, do not have bubble yet, obtain the good thin slice of surface smoothing with the thermal conductivity weighting agent that uses.The plasticity that is thin slice is good.

Then, utilize capital of a country electronic industry system: rapid thermal conductivity meter: piece number QTM-500 measures the thermal conductivity of the thin slice that obtains.The thermal conductivity of the thin slice that obtains is 3.2W/mK.Has high thermal conductivity.

Then, in order to estimate the flexibility of the thin slice that obtains, use the system ア ス カ of polymer gauge Co., Ltd. one go system sclerometer A type, 25 ℃ of duroscope hardness tests (type A test) of implementing JIS K6253 record down.Scleroscopic probe is expressed to the center of sample, makes this add pressure surface and adhere on the sample, with its 1 second with interior maximum indicator value as hardness.In addition, demonstrate that the value of hardness is more little to be rich in flexibility more.The rubber hardness of the thin slice that obtains in this embodiment is 60.

Then, in order to measure the long-term flexibility of the thin slice that obtains, in 150 ℃ baking oven, kept 3 hours.The rate of mass reduction of this moment is 0.7%.Thus, the thin slice that obtains also has long-term flexibility.

No.4-2

Except the aluminum oxide with No.4-1 makes 250 parts of (upright altogether マ テ リ ア Le corporate systems of boron nitride that thermal conductivity is 50W/mK into; Piece number BN-100) outside, the same thermally conductive materials thin slice that obtains with No.4-1 carries out various evaluations.The thin slice that obtains is not clamminess, and the phthalic acid ester of use is that aqueous softening agent is held in cross-linked polymer, becomes gelatinous resin.In addition, do not separate, relatively evenly, do not have bubble yet, obtain the good thin slice of surface smoothing with the thermal conductivity weighting agent that uses.The plasticity that is thin slice is good.The thermal conductivity of this thin slice is 3.5W/mK, has high thermal conductivity.In addition, the rubber hardness of the same ア of use ス カ one go system sclerometer A type mensuration with No.4-1 is 20.The result that the long-term flexibility of the thin slice that obtains is estimated is that rate of mass reduction is 0.8%, has long-term flexibility.

No.4-3

Except the aluminum oxide with No.4-1 changes over 700 parts of (Japan's aluminium corporate systems of aluminium nitride that thermal conductivity is 120W/mK; Piece number R-15) outside, the same thermally conductive materials thin slice that obtains with No.4-1 carries out various evaluations.The thin slice that obtains is not clamminess, and the phthalic acid of use is that aqueous softening agent is held in cross-linked polymer, becomes gelatinous resin.In addition, do not separate, relatively evenly, do not have bubble yet, obtain the good thin slice of surface smoothing with the thermal conductivity weighting agent that uses.The plasticity that is thin slice is good.The thermal conductivity of this thin slice is 3.9W/mK, has high thermal conductivity.In addition, the rubber hardness that uses ア ス カ one go system sclerometer A type to measure is 45.The result that the long-term flexibility of the thin slice that obtains is estimated is that rate of mass reduction is 0.6%, has long-term flexibility.

No.4-4

Use the compression type kneader, at normal temperatures with 39 parts of LMA, as 1 part of the polydimethyl vinylformic acid glycol ester (above-mentioned " ラ イ ト エ ス テ Le 9EG ") of polyfunctional monomer, as the tert-pentyl peroxide 3 of polymerization starter, 5,2 parts of 5-tri-methyl hexanoic acid esters (above-mentioned " カ ヤ エ ス テ Le AN "), phthalic ester are mixing 30 minutes of 60 parts in aqueous softening agent (above-mentioned " PVC ニ サ イ ザ 1 "), aluminum oxide 1300 parts (above-mentioned AS-40).Then, equally with No.4-1 use extrusion machine to be expressed between 2 the PET film and to be set as 1mm, to obtain flaky thermally conductive materials resin combination with thickness.Then, under 120 ℃, the thin slice that obtains put in the process furnace 30 minutes, the polymerization crosslinking reaction is finished.The same this thermally conductive materials thin slice of estimating with No.4-1.The thin slice that obtains does not separate with the thermal conductivity weighting agent that uses and relatively evenly, is not clamminess, and does not have bubble in addition, obtains the thin slice of surface smoothing excellence.The plasticity that is thin slice is good.The thermal conductivity of thin slice is 3.1W/mK, has high thermal conductivity.In addition, the rubber hardness that uses ア ス カ one go system sclerometer A type to measure is 62.The result that the long-term flexibility of the thin slice that obtains is estimated is that rate of mass reduction is 0.8%, has long-term flexibility.

No.5 (relatively using)

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, put into 0.3 part of 39.7 parts of 2EHA, HEA (the hydroxyl monomer of total monomer is set as 1 mole of %), 50 parts of toluene, as 0.3 part of the alpha-methyl styrene of chain-transfer agent, replace air in the container with nitrogen.Be warming up to 80 ℃, in dropping funnel, add mixture, with 2 hours times dropping as 10 parts of 0.05 part of the Diisopropyl azodicarboxylate of polymerization starter and toluene.And then add 0.01 part of Diisopropyl azodicarboxylate, and be warming up to 90 ℃, carry out polymerization in 3 hours.Before finishing, polymerization is blown into air, cooling system and polymerization is finished.Then fall toluene, obtain the polymkeric substance that contains 1 mole of % hydroxyl of solid shape carrying out underpressure distillation in the system.The Mw that has used the polymkeric substance of GPC is that 10.6 ten thousand, Mn are 5.1 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the polymkeric substance that ordinary method measures to be-60 ℃.

Then, use the compression type kneader, under 50 ℃ with 100 parts in polymkeric substance obtaining, be mixing 30 minutes of paraffin 25 parts of (above-mentioned solid paraffin 115), thermal conductivitys of 47 ℃ aluminum oxide that is 30W/mK 1300 parts (above-mentioned AS-10) as the isophorone diisocyanate of linking agent 0.65 part (amount of isocyanate that is equivalent to the hydroxyl molar weight), as 0.3 part of the dibutyl tin laurate of crosslinking accelerator, as the fusing point of thermal softening agent.Subsequently, use extrusion machine to be expressed between 2 the PET film and and be set as 1mm, obtain flaky thermally conductive materials resin combination thickness.Then, at room temperature place the flaky thermally conductive materials obtain with resin combination 24 hours, the hydroxyl in the composition and the reaction of isocyanate group are finished.The same thin slice that obtains at this moment of estimating with No.4-1.

The thin slice that obtains does not separate with the thermal conductivity weighting agent of resin and use and compares evenly, but the surface has uneven or there is the surface smoothing deterioration in bubble.The plasticity that is thin slice is bad.Thermal conductivity is 3.1W/mK, has high thermal conductivity.In addition, use ア ス カ one go system sclerometer A type to measure rubber hardness down at 25 ℃, the result surpasses as measuring 100 of boundary, can't measure, so measure under 50 ℃.Its result, the rubber hardness of this thin slice under 50 ℃ is 65.Thus, it is poor to judge the flexibility of the thin slice that obtains.And then the result that the long-term flexibility of the thin slice that obtains is estimated is that rate of mass reduction is 0.9%, has long-term flexibility, but many places produce and expand in the thin slice after mensuration.

No.4-6

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, add 38.81 parts of 2EHA, HEA 1.04 parts (the hydroxyl monomer in the total polymerization monomer is set as 4 moles of %), as the trimellitate of aqueous softening agent be 50 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 "), as 0.15 part of the α-Jia Jibenyixierjuwu of chain-transfer agent, replace air in the container with nitrogen.

Be warming up to 75 ℃, in dropping funnel, add dimethyl-2 as polymerization starter, the mixture of 0.1 part of 2 '-azo two (2 Methylpropionic acid ester) and above-mentioned aqueous softening agent 10 parts (above-mentioned " ア デ カ サ イ ザ one C880 ") was with 1.5 hours times dropping.And then adding dimethyl-2 as polymerization starter, two (the 2 Methylpropionic acid esters) 0.03 part of 2 '-azo are warming up to 90 ℃, carry out polymerization in 2 hours.

Before finishing, polymerization adds above-mentioned aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 ") 60 parts, be blown into air, cooling system and polymerization is finished, obtain containing the acrylic acid polymer of 4 moles of % hydroxyls and the mixture of aqueous softening agent (below, be called acrylic resin No.4-2).The residual 2EHA that tries to achieve by vapor-phase chromatography (GC) is 0.1%, and the multipolymer that contains 4 moles of % hydroxyls among the acrylic resin No.4-2 is 24.8%.The viscosity of acrylic resin No.2 under 25 ℃ that obtains is 2400mPas.Using the Mw of the polymkeric substance of GPC mensuration is that 37.5 ten thousand, Mn are 9.3 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the polymkeric substance that ordinary method measures to be-58 ℃.

ス リ one ワ Application モ, one one (piece number 600G) by new eastern scientific company system, under speed of rotation 300rpm, with 100 parts aforesaid propylene acid resin No.4-2,0.06 part the dibutyl tin laurate as crosslinking accelerator, 0.1 part defoamer (above-mentioned " A-515 "), 0.57 part the hexamethylene diisocyanate as linking agent (amount of isocyanate that is equivalent to the hydroxyl molar weight in the polymkeric substance), 600 parts thermal conductivity is that the aluminum oxide (above-mentioned AS-40) of 30W/mK is evenly mixing.

Then, leave standstill the resin combination that obtains and carry out deaeration in the vacuum drying apparatus of vacuum tightness being set for 0.09MPa, being coated with machine with the rod of setting is 1mm implementing to be coated with and to make its thickness on the PET film that the demoulding handles.Heat these coating things down 2 hours at 100 ℃, polymkeric substance with hydroxyl and hexamethylene diisocyanate in the said composition are reacted, obtain the thermally conductive materials thin slice.The thin slice that obtains is not clamminess, and becomes aqueous softening agent maintained gelatinous resin in cross-linked polymer.In addition, do not separate and compare evenly, obtain not having the good thin slice of surface smoothing of bubble with the thermal conductivity weighting agent that uses.That is, the plasticity of thin slice is good.The thermal conductivity of thin slice is 1.8W/mK, has high thermal conductivity coefficient.

In addition, changes in hardness and rate of mass reduction (as previously mentioned) are measured in the thermotolerance evaluation of the thin slice during as long-time (100,500,1000 hours) exposure under 130 ℃ high temperature, and it the results are shown in table 7.Hardness is that the thin slice with stacked above-mentioned thick 1mm makes thickness reach the thin slice of 10mm as working sample, with JIS K7312 7 in the hardness test Type C of record be benchmark, use the ア ス カ one go system sclerometer C type of polymer gauge Co., Ltd. system under 25 ℃, to measure.Scleroscopic probe is squeezed in the sample center, makes it add pressure surface and stick on the sample, be used as hardness with interior maximum indicator value 1 second.

The measurement result of placing the hardness after 100 hours, 500 hours, 1000 hours from initial stage hardness, in being heated to 130 ℃ baking oven calculates changes in hardness, the value and the changes in hardness of expression initial stage hardness in table 7.The negative value that demonstrates changes in hardness slows down.If changes in hardness, rate of mass reduction are less, represent that then the thermotolerance of thin slice is good, can bring into play long-time stable heat dissipation characteristics.In addition, this thermotolerance evaluation be to above-mentioned No.4-1～4-4 and relatively the No.4-5 of usefulness carry out, the result and the note in table 7.

No.4-7

In No.4-6, making the dibutyl tin laurate as crosslinking accelerator is 0.01 part for 0.06 part, as the compound that has the atom that lone electron pair is arranged at intramolecularly, uses N, N, N ', N '-tetramethyl--1,6-hexanediamine (eastern ソ one Co., Ltd.'s system; " TOYOCAT-MR ") 0.1 part, in addition the same with No.4-6, obtain the thermally conductive materials thin slice.The plasticity of thin slice is the same with No.4-6 good, and thermal conductivity is 1.8W/mK.The thermotolerance evaluation result is shown in table 7.

No.4-8

In No.4-7, will have the compound of the atom that lone electron pair is arranged at intramolecularly, become N, N, N '-trimethylammonium amino-ethyl carbinolamine (eastern ソ one Co., Ltd.'s system; " TEDA-RX5 ") 0.5 part, in addition the same with No.4-7, obtain the thermally conductive materials thin slice.The plasticity of thin slice is the same with No.4-7 good, and thermal conductivity is 1.9W/mK.The thermotolerance evaluation result is shown in table 7.

No.4-9

In No.4-7, will have the compound of the atom that lone electron pair is arranged at intramolecularly, become 0.5 part of hexamethylphosphoramide, in addition the same with No.4-7, obtain the thermally conductive materials thin slice.The plasticity of thin slice is the same with No.4-7 good, and thermal conductivity is 1.7W/mK.The thermotolerance evaluation result is shown in table 7.

No.4-10

In No.4-7, will have the compound of the atom that lone electron pair is arranged at intramolecularly, become 0.5 part of methyl ethyl diketone, in addition the same with No.4-7, obtain the thermally conductive materials thin slice.The plasticity of thin slice is the same with No.4-7 good, and thermal conductivity is 1.7W/mK.The thermotolerance evaluation result is shown in table 7.

From above-mentioned table 7 as can be known, the resin combination that example of the present invention can obtain thermal conductivity, flexibility effectively, the thermally conductive materials that has excellent formability is used.On the other hand as can be known, the oily mater as liquid under not using normal temperature uses relatively using among the No.4-5 of thermal softening agent, with the routine ratio mutually of the present invention.In addition, by using the compound that has the atom that lone electron pair is arranged at intramolecularly, the hardness that can suppress gelatinous resin reduces.

Experiment 5 (experiment of the resin combination when relevant polymkeric substance (I) is bridging property polymkeric substance (I-b))

Synthesis example 6

In the container that possesses thermometer, agitator, gas introduction tube, reflux exchanger and dropping funnel, add 39.22 parts of 2EHA, vinylformic acid 2-hydroxyl ethyl ester 0.78 part of (monomer with hydroxyl in the total polymerization monomer is set as 3 moles of %), trimellitate and be 50 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 "), as 0.15 part of the α-Jia Jibenyixierjuwu of chain-transfer agent, replace air in the container with nitrogen.Be warming up to 75 ℃, in dropping funnel, add dimethyl 2 as polymerization starter, 0.1 part of 2 '-azo two (2 Methylpropionic acid ester) and trimellitate were the mixture of 10 parts in aqueous softening agent (above-mentioned " ア デ カ サ イ ザ one C880 "), with 1.5 hours times dropping.And then adding dimethyl 2 as polymerization starter, two (the 2 Methylpropionic acid esters) 0.03 part of 2 '-azo are warming up to 90 ℃, carry out polymerization in 2 hours.

Added before polymerization is finished as 0.05 part of the dibutyl tin laurate of organometallic compound, be blown into air, cooling system and polymerization is finished obtains (methyl) acrylic resin (below, be called resin 5-A).The residual 2EHA that obtains by vapor-phase chromatography (GC) is 0.1%, and the polymkeric substance that contains 3 moles of % hydroxyls among the resin 5-A is 39.9%.Viscosity under 25 ℃ of the resin 5-A that obtains is 6100mPas.With regard to the molecular weight that uses the polymkeric substance that GPC measures, weight-average molecular weight Mw is 35.6 ten thousand, and number-average molecular weight Mn is 9.1 ten thousand.In addition, use differential scanning calorimetry and adopt the second-order transition temperature of the polymkeric substance that ordinary method measures to be-60 ℃.

No.5-1

Utilize ス リ one ワ Application モ, one one (piece number 600G) of new eastern scientific company system, under speed of rotation 300rpm, with 100 parts resin 5-A, 0.1 part defoamer (above-mentioned " A-515 "), 0.57 part 1, hexamethylene-diisocyanate (with respect to the amount of hydroxyl groups in the polymkeric substance, being 1.0 normal amount of isocyanate), 0.25 part the acetic acid as acidic cpd (119 ℃ of boiling points), 200 parts thermal conductivity are aluminum oxide (clear and electrician's corporate system of 30W/mK; Piece number AS-10) evenly mixing.Working life, deaeration under the viscosity of measuring the resin combination obtain under the condition as follows, 25 ℃, the result is as shown in table 8.

[viscosity]

Use Brookfield viscometer under the condition of rotor N0.4 rotating speed 6rpm, to measure the viscosity of resin combination under 25 ℃ that obtains.If low viscosity, for example operation is excellent and the effect of heat radiation (heat conduction) performance of improving the cured article that obtains is filled, had to height that can carry out the thermal conductivity weighting agent, can give easy deaeration performance in addition, so that can remove the air that when making resin combination, contains easily by structure.

[working lives under 25 ℃]

The resin combination that keeping obtains in the tank of temperature adjustment to 25 ℃, carrying out viscosimetric analysis under the situation identical through time ground, will confirm that viscosity rises time more than 20% as measuring working life (serviceable time) from the initial stage viscosity number with the condition of viscosimetric analysis.But, its viscosity rose less than 10% o'clock after having passed through 8 hours, was evaluated as more than 8 hours.For example, if the serviceable time is longer, can a mass production, the cost-effectivenes excellence.

[deaeration]

In the vacuum drying apparatus of vacuum tightness being set for 0.09MPa, leave standstill the resin combination that obtains, the existence of the bubble that contains in the resin combination that visual observation is implemented the deaeration operation respectively 2 minutes, 5 minutes, 10 minutes the time.When confirming not have bubble to exist for visual time, be not judged as zero, even in the time still can confirming, be judged as on a small quantity *.For example, if do not confirm to exist bubble by the deaeration operation of short period of time, the productivity excellence.

Then, the resin combination that obtains is carried out the deaeration of 2 minutes and 10 minutes under deaeration condition as follows, being coated with machine with the rod of setting is 1mm with the material separate application that obtains implementing on the PET film that the demoulding handles and making its thickness.Then, heated these coating things down 2 hours, polymkeric substance that contains hydroxyl and hexamethylene diisocyanate in the said composition are reacted, obtain the laminar cured article of this resin combination at 100 ℃.Similarly the plasticity of the thin slice that obtains this moment is estimated with above-mentioned experiment 1.The results are shown in table 8.And then the thin slice that obtains about the deaeration time was made as 10 minutes is similarly estimated initial stage hardness, thermotolerance, the weather resistance of initial stage thermal conductivity, thin slice with above-mentioned experiment 1.In addition, stable on heating evaluation was carried out under 100 ℃ * 168 hours.The results are shown in table 8.

No.5-2

In No.5-1, except acidic cpd was become 0.25 part of propionic acid (141 ℃ of boiling points) from acetic acid, all the other were the same with No.5-1, obtain the laminar cured article of resin combination and this resin combination.In addition, estimate the same with No.5-1, the result is as shown in table 8.

No.5-3

In No.5-1, except the thermal conductivity weighting agent is become 300 parts from 200 parts, all the other are the same with No.5-1, obtain the laminar cured article of resin combination and this resin combination.In addition, estimate the same with No.5-1, the result is as shown in table 8.

No.5-4 (relatively using)

In No.5-1, except not using the acidic cpd, all the other are the same with No.5-1, obtain the laminar cured article of resin combination and this resin combination.In addition, estimate the same with No.5-1, the result is as shown in table 8.The resin combination that obtains is compared with any example of the present invention, and viscosity is higher and operation is poor, and deaeration needs considerable time fully, and working life is short.Therefore, even compare with any example of the present invention, its result produces rate variance and cost up.

The plasticity of the cured article when in addition, the deaeration time being made as 2 minutes is poor.Think that this is to be caused by the influence of air bubbles that exists in cured article.

No.5-5 (relatively using)

In No.5-1, do not use acidic cpd, and the thermal conductivity weighting agent is become 300 parts from 200 parts, in addition, all the other are the same with No.5-1, obtain the laminar cured article of resin combination and this resin combination.In addition, estimate the same with No.5-1, the result is as shown in table 8.It is bad that the dispersion of weighting agent appears in the resin combination that obtains, and compare with any example of the present invention, and viscosity higher (surpass the mensuration upper limit of machine, can't measure) is even also think have bubble to exist the deaeration time being made as under 10 minutes the situation.In addition, all lack than any one example of the present invention working life.Therefore, its result produces rate variance and cost up.And then, confirm that the shaping of cured article is poor, heat conductivility is also low.Think that this is to be caused by the influence of air bubbles that exists in cured article.

Wherein, the abbreviation that uses in table 8 is as follows.

HDI:1, hexamethylene-diisocyanate

A-515: PVC _StarNetwork ケ ミ one corporate system, defoamer; Trade(brand)name " A-515 "

△ hardness: the difference of hardness of the thin slice hardness value behind thin slice initial stage hardness value and the thermal test

Table 8 (experiment 5)

No.	5-1	5-2	5-3	5-4	5-5
						Resin 5-A HDI A-515 acetate propionate aluminum oxide	100 0.57 0.1 0.25 0 200	100 0.57 0.1 0 0.25 200	100 0.57 0.1 0.25 0 200	100 0.57 0.1 0 0 200	100 0.57 0.1 0 0 200
Viscosity (Pas)	20.5	21.5	46.9	50.2	Can't measure
						Deaeration 2 minutes 5 minutes 10 minutes	○ ○ ○	○ ○ ○	○ ○ ○	× × ○	× × ×
Working life (25 ℃)	More than the 8hr	More than the 8hr	More than the 8hr	1hr	0.5hr
						Thin slice plasticity 2 minutes 10 minutes	○ ○	○ ○	○ ○	×1 ○	×2 ×2
Thin slice initial stage hardness (C type)	12	11	23	12	30
						Thin slice initial stage thermal conductivity (W/mK)	0.85	0.81	1.20	0.85	0.95
Thermotolerance rate of mass reduction (%) thin slice hardness (C type) thermal conductivity W/mK)	0.15 12 0.88	0.12 12 0.82	0.11 25 1.23	0.12 13 0.82	0.13 33 0.91
						Weather resistance (△ hardness)	0	1	2	1	3

* 1: have uneven or bubble at slice surfaces.

* 2: aqueous softening agent is in surface isolation, or separation, the sedimentation of weighting agent occur.

As shown in Table 8, operation or the productivity excellence of example of the present invention when obtaining thermally conductive materials with composition, and can obtain the cured article (thermally conductive materials) of the thermally conductive materials of plasticity, flexibility, thermal conductivity, excellent in te pins of durability expeditiously with composition.On the other hand, in any comparative example, compare with example of the present invention, operation or productivity when it obtains thermally conductive materials with composition are all poor, and the cured article that obtains is also poor aspect plasticity, thermal conductivity.

Industrial utilizability

The resin combination of the application of the invention can successfully obtain the thermally conductive materials of thermal conductivity, flexibility excellence. Therefore, such as being used between the heater element such as electrical and electronic parts and radiators such as thermoreceptor, fin, metallic heat radiating plate and the thermally conductive materials that the heating of electrical and electronic parts etc. is dispelled the heat is useful. In addition, can be applied to other thermally conductive materials purposes.

Claims (10)

1. thermally conductive materials resin combination, be to contain the thermally conductive materials resin combination that (methyl) acrylic acid polymer (I-a) or (methyl) acrylic acid series bridging property polymkeric substance (I-b), aqueous softening agent (II) and thermal conductivity are the above thermal conductivity weighting agent (III) of 20W/mK, wherein

Described aqueous softening agent (II) rate of mass reduction when keeping 24 hours for liquid and under 130 ℃ down for 25 ℃ is below the 2 quality %,

Described thermal conductivity weighting agent (III) is 100～1500 mass parts with respect to 100 mass parts (methyl) acrylic acid polymer (I-a) or (methyl) acrylic acid series bridging property polymkeric substance (I-b),

Described thermally conductive materials also contains polymerizable monomer (IV) with resin combination under the situation that contains (methyl) acrylic acid polymer (I-a), and when the total amount of (methyl) acrylic acid polymer (I-a), aqueous softening agent (II) and polymerizable monomer (IV) is made as 100 quality %, (methyl) acrylic acid polymer (I-a) is 10～60 quality %, aqueous softening agent (II) is 5～60 quality %, polymerizable monomer (IV) is 30～85 quality %

Described thermally conductive materials with resin combination under the situation that contains (methyl) acrylic acid series bridging property polymkeric substance (I-b), also contain can with the linking agent (VI) of (methyl) acrylic acid series bridging property polymkeric substance (I-b) reaction, and when the total amount of (methyl) acrylic acid series bridging property polymkeric substance (I-b) and aqueous softening agent (II) is made as 100 quality %, (methyl) acrylic acid series bridging property polymkeric substance (I-b) is 10～50 quality %, and aqueous softening agent (II) is 50～90 quality %.

2. thermally conductive materials resin combination as claimed in claim 1, wherein,

The viscosity of described aqueous softening agent (II) under 25 ℃ is below the 1000mPas.

3. thermally conductive materials resin combination as claimed in claim 1, wherein,

Described (methyl) acrylic acid polymer (I-a) is by the material of radical polymerization in aqueous softening agent (II).

4. thermally conductive materials resin combination as claimed in claim 1, wherein,

Described (methyl) acrylic acid polymer (I-a) has the second-order transition temperature below 0 ℃, and at least a portion of described polymerizable monomer (IV) is that the carbonatoms of alkyl is (methyl) alkyl acrylate of 2～18.

5. thermally conductive materials resin combination as claimed in claim 1, wherein,

And then also contain radical polymerization initiator (V).

6. thermally conductive materials resin combination as claimed in claim 1, wherein,

Described (methyl) acrylic acid series bridging property polymkeric substance (I-b) is to make polymerizable monomer (I-b-1) and have the material that polymerizable monomer (I-b-2) copolymerization that is used for crosslinked functional group obtains, with respect to 100 moles of % of total amount of polymerizable monomer (I-b-1) and polymerizable monomer (I-b-2), polymerizable monomer (I-b-2) is 0.01～5 mole of %.

7. thermally conductive materials resin combination as claimed in claim 6, wherein,

The functional group of described polymerizable monomer (I-b-2) is a hydroxyl, described linking agent (VI) is the compound with isocyanate group, catalyzer as being used to this linking agent (VI) and described (methyl) acrylic acid series bridging property polymkeric substance (I-b) are reacted further has the compound that has the atom that lone electron pair is arranged in organometallic compound and the molecule.

8. thermally conductive materials resin combination as claimed in claim 1 wherein, further also contains acidic cpd.

9. thermally conductive materials, wherein,

Any described thermally conductive materials is solidified with resin combination and obtain.

10. thermally conductive materials as claimed in claim 9, wherein,

Rate of mass reduction when keeping 168 hours down for 130 ℃ is below the 5 quality %.