JP5857785B2 - Thermally conductive insulating resin composition and thermally conductive adhesive sheet - Google Patents

Description

  The present invention relates to a heat conductive insulating resin composition used for a heat conductive sheet used for releasing heat generated from an electronic device or the like.

In recent years, the development of the electronics field has been remarkable, and in particular, electronic devices have become smaller, lighter, higher density, and higher in output, and demands for these performances have become increasingly sophisticated.
In order to increase the density of electronic circuits, high insulation reliability and miniaturization are required. And the problem of the high temperature by heat_generation | fever by high output of an electronic device becomes remarkable, and the request | requirement with respect to heat dissipation improvement is high.

In the electronics field, polymer materials are used as insulating materials. Therefore, in order to improve heat dissipation, it has become desirable to improve the thermal conductivity of polymer materials. However, since there was a limit to the improvement of the thermal conductivity of the polymer material, the heat dissipation of the insulating material was improved by combining a high thermal conductivity filler. However, in addition to the demand for improvement in heat dissipation for electronic devices, the demand for improvement in insulation reliability is also high, and there has been a demand for polymer materials that take into account the above-mentioned physical properties.

Therefore, in order to solve these requirements, for example, a polymer composition mainly composed of an acid value-containing polyester / polyurethane and an epoxy resin is disclosed (see Patent Document 1). Moreover, the resin composition containing a polyimide siloxane, both terminal epoxy siloxane, and a hardening | curing agent is disclosed (refer patent document 2). In addition, a thermosetting resin composition containing an epoxy resin, an NBR rubber containing as little ionic impurities as possible, and a nitrogen-containing phenol novolac resin as a main component is disclosed (see Patent Document 3). Also disclosed is a resin composition containing an epoxy resin, a phenol resin, a curing accelerator for epoxy resin, and an elastomer (see Patent Document 4). In addition, a proposal has been made focusing on hydrogenated polybutadiene skeleton (Patent Document 5).

JP-A-11-116930 JP 2007-51212 A JP 2004-91648 A JP 2007-161811 A JP 11-114733 A

However, in Patent Document 1, although it was a polymer material having good heat conduction characteristics, it was not possible to achieve both a high level of insulation reliability and heat resistance.

Further, in Patent Document 2, although the polymer material has flexibility and peculiar heat resistance to the siloxane resin, the siloxane skeleton itself has poor adhesion to the base material, so that it is cured with epoxysiloxane having a low crosslinking density. However, there was a problem that sufficient adhesive strength could not be obtained, and in addition, there was a problem of poor workability that many protrusions occurred when thermosetting by a hot press.

Further, in Patent Document 4, there is a problem that the adhesive strength is poor because an elastomer-derived polymer material is used.

In Patent Document 5, since a composite resin composed of a carboxyl group-containing hydrogenated polybutadiene resin and an acrylic resin having an epoxy group is used, excellent flexibility derived from a hydrogenated polybutadiene skeleton, and adhesion to copper Have However, since ester skeleton is introduced when synthesizing composite resin, insulation reliability and chemical resistance after exposure to high temperature and high humidity,
There was a problem in basic characteristics as an insulating material for general electric circuits.

An object of the present invention is to provide a heat conductive insulating resin composition having adhesive properties, solder heat resistance and insulation reliability, and a heat conductive adhesive sheet.

In order to solve the above problems, it is composed of a polyester resin, an epoxy curing agent, a heat conductive insulating filler, etc., in which a cyclic structure such as an aromatic ring or an aliphatic ring is directly incorporated next to the ester bond in the main chain. A heat conductive insulating resin composition was invented.

According to the present invention configured as described above, the ester bond of the polyester resin is protected by the presence of a bulky cyclic structure, and is not easily decomposed during heating. Therefore, the heat resistance could be improved while maximizing the insulation reliability of the polyester resin. Further, by combining the polyester resin and the epoxy curing agent, it was possible to improve the adhesive properties while achieving solder heat resistance. As a result, it was possible to provide a thermally conductive insulating resin composition having adhesive properties, solder heat resistance and insulation reliability, and a thermally conductive adhesive sheet using the composition.

In the present invention, it is important that the addition-type polyester resin (A) has a cyclic structure next to the ester bond in the main chain. Since the ester bond can be protected with a bulky cyclic structure at a high temperature, insulation reliability, heat resistance, etc. can be remarkably improved as compared with the case of using a general condensed polyester resin.

The addition type polyester resin (A) is, for example, an addition type polyester resin (A-1) obtained by reacting a polyol compound (a) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. Is preferably used.

In the present invention, the polyol compound (a) has two or more hydroxyl groups, and further has a repeating unit having a polymerization degree of 2 or more in its structure. As the polyol compound (a), for example, polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polysiloxane polyols are preferable. The polyol compound (a) preferably has a weight average molecular weight of 500 to 50,000. In the present invention, the weight average molecular weight refers to gel permeation chromatography (hereinafter referred to as “gel permeation chromatography”).
It is also referred to as “GPC”) and means a weight average molecular weight in terms of polystyrene as measured.

Examples of polyester polyols include polyester polyols obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component. Among the polyfunctional alcohol components, the diol includes ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol. -3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol -L, 2-ethyl-1,3-hexanediol, cyclohexanediol,
Bisphenol A etc. are mentioned. Examples of the polyfunctional alcohol component having three or more hydroxyl groups include trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol Mannitol, arabitol, xylitol, galactitol, glycerin and the like. Moreover, the polyester polyol which has a phosphorus atom can also be used, specifically, 2- (9,10-dihydro-9-oxa-10-phosphaphenanthren-10-yl) methylsuccinic acid or its acid anhydride. And ethylene glycol or 2- (9,10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl)-
The polyester polyol obtained by ester or its polycondensation is mentioned.

Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid,
Examples thereof include aliphatic or aromatic dibasic acids such as phthalic anhydride, isophthalic acid and trimellitic acid, and anhydrides thereof.

Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

Polycarbonate polyols have a structure represented by the following general formula (1) in the molecule.

General formula (1)
− [— O—R ⁸ —O—CO—] _m —

(In the formula, R ⁸ represents a divalent organic residue, and m represents an integer of 1 or more.)

The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

Specific examples of the glycol or bisphenol used in the production methods of (1) and (2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanedio- 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol,
Cyclohexanediol, bisphenols such as bisphenol A and bisphenol F, bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the bisphenols, and the like can also be used. These compounds can be used as one kind or a mixture of two or more kinds.

Examples of polyether polyols include polymers, copolymers, and graft copolymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, propylene oxide, and butylene oxide; hexanediol, methylhexanediol, heptanediol. Polyether polyols obtained by condensation of octanediol or mixtures thereof; aromatic polyols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenol A and bisphenol F; Trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol,
Polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide synthesized using polyhydric alcohols such as sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, etc. as part of the raw material A block copolymer or a random copolymer, a polytetramethylene glycol, a block copolymer of tetramethylene glycol and neopentyl glycol, or a polyether polyol such as a random copolymer, having two or more hydroxyl groups Can be used.

Examples of polybutadiene polyols include those obtained by hydrogenating unsaturated bonds in the molecule, such as polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, etc. Is mentioned.

Examples of polysiloxane polyols include compounds represented by general formulas (2) and (3).
General formula (2)

(X represents a hydroxyl group, R ^1, R ² each represent an alkylene group having 1 to 6 carbon atoms, n is
Represents an integer of 5 or more. )
General formula (3)

(Y represents a hydroxyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴ , R ⁵ and R ⁶ are each an alkylene group having 1 to 6 carbon atoms, and R ⁷ is a hydrogen atom or 1 to 1 carbon atoms. Represents an alkyl group of 6, n
Represents an integer of 5 or more. )

Among these polyol compounds (a), 1,4-cyclohexanedicarboxylic acid and 3-
Polyester polyol composed of methyl-1,5-pentanediol, polycarbonate polyol using only 1,6-hexanediol as glycol, 1,6-hexanediol and 3-methyl-1,5 Polycarbonate diols using pentanediol as glycol, polycarbonate diols using 1,9-nonanediol and 2-methyl-1,8-octanediol as glycol, poly Tetramethylene glycol, polypropylene glycol, or a copolymer polyether polyol of tetramethylene glycol and neopentyl glycol, polybutadiene polyol,
Hydrogenated polybutadiene polyol, polysiloxane polyol, etc. are excellent in flexibility, heat resistance, and hydrolysis resistance of the main chain skeleton. For example, when used in a heat conductive adhesive sheet, insulation reliability, flexibility, heat resistance It is particularly preferable because of its excellent moisture resistance. These polyol compounds (a) may be used alone or in combination.

In addition to the above polyols, it is also preferable to use a trifunctional polyol as the polyol compound (a). Since the addition type polyester resin (A) has a branched structure, when it is used as a heat conductive insulating layer of a heat conductive adhesive sheet, the cohesive strength of the layer increases and the heat resistance is improved. It can be improved.

Trifunctional polyols include, for example, polyhydric alcohols such as trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin and the like. Compounds. Among these, it is preferable to use trimethylolpropane or pentaerythritol in terms of reaction control.

Compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring in the present invention [hereinafter,
Compound (b) is preferably a compound having an alicyclic ring or a compound having an aromatic ring, more preferably an alicyclic dibasic acid anhydride or an aromatic dibasic acid anhydride. Compound(
When a compound other than b) is used, a certain degree of adhesive strength and heat resistance can be obtained due to the substrate adhesion and heat resistance due to the polarity derived from the ester bond, but still higher temperature and humidity (for example, temperature:
The insulation reliability is poor under severe conditions such as 85 ° C. and humidity (85%), and the heat resistance cannot satisfy a higher degree of solder heat resistance such as a high-temperature solder test or a solder test in a humidified state.

Compounds having an alicyclic ring are, for example, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, still end. Examples thereof include styrene tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.

Examples of the compound having an aromatic ring include phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, and the like.

Among these compounds (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl Nadic anhydride, hydrogenated methyl nadic anhydride, and the like are particularly preferable from the viewpoints of insulation reliability and solder heat resistance because ester bonds can be more effectively protected.

The addition-type polyester resin (A) is preferably an addition-type polyester resin (A-1) described below. That is, the synthesis of the addition-type polyester resin (A-1) is carried out by using a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring when the total hydroxyl group of the polyol compound (a) is 1 mol. ) Is preferably reacted at a ratio of 0.7 mol to 1.3 mol, more preferably 0.9 mol to 1.1 mol.
When the total of acid anhydride groups is less than 0.7 mol, the resulting addition-type polyester resin (A)
There is a risk that the amount of the carboxyl group of the resin is insufficient in heat resistance due to insufficient crosslinking with the epoxy curing agent. In addition, the reaction with the compound (c) having two or more epoxy groups, which will be described later, is difficult to cause a sufficient reaction, and the weight average molecular weight of the addition type polyester resin (A) may be insufficient.
In addition, even when the total amount of acid anhydride groups is more than 1.3 mol, there may be many side reactions when reacting with the compound (c) having two or more epoxy groups, which may cause gelation during the reaction. is there.

Known synthesis conditions can be used for the synthesis of the addition type polyester resin (A-1).
For example, a polyol compound (a) and a solvent are charged into a flask, and 20 to 1 under a nitrogen stream.
After uniformly dissolving by heating and stirring at 20 ° C, the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is added, and added by heating at 50 to 150 ° C while stirring. Type polyester resin (A-1) can be obtained. In addition, before adding the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring, the polyol compound (a) and the solvent charged in the flask in advance are heated and stirred at 100 ° C. or higher, and the solvent A part of the solvent may be removed. This operation is usually performed to remove water (dehydration treatment) in the system, and when the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is reacted by this operation, The ring opening reaction of the acid anhydride group due to can be suppressed.

In the present invention, the addition type polyester resin (A) is an addition type polyester resin (A-1).
To an addition type polyester resin obtained by reacting a compound (c) having two or more epoxy groups (
More preferably, it is A-2). Adhesive strength can be further improved by appropriately selecting the compound (c) having two or more epoxy groups.

In the present invention, the compound (c) having two or more epoxy groups may be a compound containing two epoxy groups in the molecule. Specifically, the compound (c) having two or more epoxy groups is, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin. Type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone Diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A-type diglycidyl ether, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol-furful orange glycidyl ether, bis Phenoxyethanol full orange glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyl toluidine, JP 2004-156024 A, special Epoxy compounds excellent in flexibility disclosed in Japanese Unexamined Patent Application Publication Nos. 2004-315595 and 2004-323777, and the following formula ( ) - (epoxy compounds represented by structure 3) and the like.
Chemical formula (4)

化学式（５）

Chemical formula (5)

化学式（６）

Chemical formula (6)

Among these, 1,6-hexanediol diglycidyl ether can further improve the flexibility of the addition type polyester resin (A-2). The bisphenol A / epichlorohydrin type epoxy resin can further improve the heat resistance of the addition type polyester resin (A-2). The compound (c) having two or more epoxy groups can be selected according to the purpose, and these may be used alone or in combination.

When synthesizing the addition type polyester resin (A-2), the addition type polyester resin (A-
The ratio in which 1) and the compound (c) having two or more epoxy groups are reacted is such that when the total of carboxyl groups of the addition type polyester resin (A-1) is 1 mol, two or more epoxy groups are reacted. It is preferable to react the epoxy group in the compound (c) having a ratio of 0.5 mol to 1.5 mol, and it is more preferable to react in a proportion of 0.7 mol to 1.3 mol. Addition finally obtained when the proportion of the epoxy group in the compound (c) having two or more epoxy groups is less than 0.5 mol with respect to 1 mol of the carboxyl group of the addition-type polyester resin (A-1) Since the molecular weight of the type polyester resin (A-2) is low, the heat resistance tends to be reduced, and it is difficult to form a heat conductive insulating layer. Moreover, when the ratio of the epoxy group in the compound (c) having two or more epoxy groups is more than 1.5 mol with respect to 1 mol of the carboxyl group of the addition type polyester resin (A-1), When the amount of the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is reacted in the final synthesis stage, a large number of side reactions may occur and gelation may occur during the synthesis.

The addition type polyester resin (A-2) can be synthesized using known synthesis conditions. For example, an addition-type polyester resin (A-1), a compound (c) having two or more epoxy groups, and a solvent are charged into a flask and heated at 100 to 150 ° C. with stirring to add the addition-type polyester resin (A- 2) can be obtained. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

In the present invention, the addition type polyester resin (A) is an addition type polyester resin (A-2).
And a compound (b) having a saturated or unsaturated ring structure and an acid anhydride ring (hereinafter referred to as compound (b)
It is more preferable that the addition-type polyester resin (A-3) be reacted with. The addition-type polyester resin (A-2) has a hydroxyl group in the side chain, and a carboxyl group is generated in the side chain by reacting the hydroxyl group with the acid anhydride group of the compound (b). The heat resistance can be further improved by a crosslinking reaction between the carboxyl group and the epoxy curing agent. In addition, the presence of a bulky cyclic structure adjacent to the ester bond on the side chain makes it difficult for the ester bond on the side chain to be decomposed at high temperatures, thereby improving the heat resistance.

Addition type polyester resin (A-2) when synthesizing addition type polyester resin (A-3)
The compound (b) is reacted with the compound having a saturated or unsaturated cyclic structure and an acid anhydride ring when the total number of hydroxyl groups of the addition-type polyester resin (A-2) is 1 mol. The acid anhydride group in b) is preferably reacted at a rate of 0.05 mol to 0.95 mol, more preferably at a rate of 0.1 mol to 0.9 mol. When the ratio of the acid anhydride group in the compound (b) is less than 0.05 mol relative to 1 mol of the hydroxyl group in the addition-type polyester resin (A-2), the amount of carboxyl groups that can be introduced into the main chain is small. The effect of improving the heat resistance after the crosslinking reaction tends to be difficult to find. On the other hand, when the amount is more than 0.95 mol, the amount of carboxyl groups in the finally obtained addition-type polyester resin (A) tends to be excessive, and the adhesive strength tends to decrease.

In the present invention, the synthesis of the addition type polyester resin (A-3) can be carried out using known synthesis conditions. For example, addition type polyester resin (A-2), compound (b) in a flask
The addition-type polyester resin (A) can be obtained by charging the mixture and the solvent and heating at 50 to 100 ° C. with stirring. This reaction proceeds even in the absence of a catalyst, but if necessary 3
A catalyst such as a secondary amino group-containing compound may be used.

In the present invention, the acid value of the addition-type polyester resin (A) is preferably 1 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g. When the acid value is less than 1 mgKOH / g, since there are few carboxyl groups, various physical properties after curing may be reduced. On the other hand, if the acid value exceeds 100 mgKOH / g, the heat conductive insulating layer becomes too hard and the adhesive strength may be insufficient. In addition, in the range of 1-100 mgKOH / g acid value, 1 mgKOH
When designing in a range close to / g, the flexibility and adhesion of the resulting coating film tend to be improved.
On the other hand, when designing in a range close to 100 mgKOH / g, the number of crosslinking points increases, so the heat resistance of the finally obtained coating film tends to be improved.

In the present invention, the weight average molecular weight of the addition-type polyester resin (A) is 5000 to 500.
000 is preferable, and 10,000 to 300,000 is more preferable. Weight average molecular weight is 500
If it is less than 0, solder heat resistance and flexibility may be insufficient. On the other hand, when the weight average molecular weight exceeds 500,000, the viscosity of the heat conductive insulating resin composition becomes too high, and thus the coating property may be lowered. When the weight average molecular weight is designed to be close to 5000 within the range of 5000 to 500000, the end of the resulting resin (ie, carboxyl group)
Since there are many, since resin rich in crosslinkability is obtained, it exists in the tendency for the heat resistance of a heat conductive insulating layer to improve. On the other hand, when designing with a value close to 500,000, the heat conductive insulating layer tends to be excellent in adhesion and flexibility.

In the addition type polyester resin (A) of the present invention, when synthesizing the ester bond of the main chain, a compound having one or more hydroxyl groups other than the polyol compound (a) or a functional group other than the hydroxyl group as an optional component. The compound which has can be used.

The compound having one or more hydroxyl groups other than the polyol compound (a) includes a monoalcohol compound (a-1-1) and a diol compound (a-1-2) having two hydroxyl groups in the molecule. ), A compound (a-1-3) having 3 or more hydroxyl groups in the molecule is preferred. These compounds may have a crosslinkable functional group other than a hydroxyl group in the molecule.

The monoalcohol compound (a-1-1) includes, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol
Aliphatic monoalcohols such as ruthel, lauryl alcohol and stearyl alcohol; Alicyclic monoalcohols such as cyclohexanol; Aromatic monoalcohols such as benzyl alcohol and fluorenol; Phenol Phenols such as methoquinone; monoalcohol compounds having functional groups other than hydroxyl groups, such as hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, 2-hydroxyethyl (meth) acrylate ("2- “Hydroxyethyl acrylate” and “2-hydroxyethyl methacrylate” are collectively referred to as “2-hydroxyethyl (meth) acrylate. The same shall apply hereinafter.), 4-hydroxybutyl (meta ) Hydroxyl group-containing (meth) acrylate compounds such as acrylate and glycidyl Sill group-containing epoxy compound, Okisetan'aruko - hydroxyl group-containing oxetane compound such as Le, and the like. Other examples include oligomer-type monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and caprolactone addition polymer using monoalcohol as an initiator. Among these, considering the reactivity and reaction control of the hydroxyl group, lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol,
2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate
Is preferred.

In the present invention, when the monoalcohol compound (a-1-1) is used, the end of the addition-type polyester resin (A) can be sealed, so that the low-molecular-weight addition-type polyester resin (A
) Can be suitably used when it is necessary to adjust the weight average molecular weight.
In addition, when the monoalcohol compound (a-1-1) has a crosslinkable functional group other than a hydroxyl group, a functional group other than a carboxyl group can be introduced into the terminal of the addition-type polyester resin (A). It can be suitably used when terminal modification of the addition type polyester resin is required.

Diol compounds (a-1-2) having two hydroxyl groups in the molecule are, for example, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol,
-Methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2- Butyl-2-
Methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol
3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,3,5-trimethyl-1, 3-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, propanediol, 1,3-butanediol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2
-Ethyl-1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimerdiol, hydrogenated bisphenol A, spiroglycol Aliphatic or cycloaliphatic geo-
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-
Methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-
Dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-
Isopropylidenephenol, 1,2-indandiol, 1,3-naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9'-bis (4-hydroxyphenyl) ) Aromatic diols such as fluorene and 9,9′-bis (3-methyl-4-hydroxyphenyl) fluorene. Other examples include sulfur atom-containing diols and bromine atom-containing diols.

A compound having a functional group other than a hydroxyl group is preferably a tertiary amino group, a carboxyl group or the like as the functional group.

The compound containing a tertiary amino group is, for example, N, N-bis (2-hydroxypropyl).
Aniline, N, N-bis (2-hydroxyethyl) aniline, N, N-bis (2-hydroxyethyl) methylamine, N, N-bis (2-hydroxyethyl) propylamine, N
, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N, N-bis (2-hydroxyethyl) octylamine, N, N-
Bis (2-hydroxyethyl) benzylamine, N, N-bis (2-hydroxyethyl)
Examples include tertiary amino group-containing diol compounds such as cyclohexylamine. Among these, when N, N-bis (2-hydroxypropyl) aniline or the like is used, it is preferable in that heat resistance can be further improved while maintaining flexibility by increasing the cohesive force of the heat conductive insulating layer. .

Examples of the compound containing a carboxyl group include dimethylolbutanoic acid, dimethylolpropionic acid, 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol and the like. Is mentioned. Among these, when dimethylolbutanoic acid or dimethylolpropionic acid is used, the number of carboxyl groups at the end of the main chain of the addition-type polyester resin (A) can be increased. Therefore, when the addition type polyester resin (A-1) is reacted with the compound (c) having at least two epoxy groups in one molecule, it tends to be able to synthesize a higher weight average molecular weight.

Here, the polyol compound (a) and the hydroxyl group-containing compound (a-1) can be used in any ratio according to the purpose in the present invention, and with respect to 1 mol of the hydroxyl group in the polyol compound (a), The hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of 0.01 mol to 1 mol, preferably 0.05 mol to 0.5 mol. Polyol compound (
When the hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of less than 0.01 mol with respect to 1 mol of the hydroxyl group in a) (that is, when the polyol compound (a) is used alone), The polyol compound (a) alone can exhibit sufficient insulation reliability, heat resistance, and adhesive strength, but it is difficult to obtain higher heat resistance. Moreover, when more than 1 mol, the cohesive force of the coating film finally obtained will increase too much, and it exists in the tendency for adhesive strength to fall.

In the present invention, the epoxy curing agent (B) is not particularly limited as long as it is a compound containing two or more epoxy groups in the molecule.

Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, Bisphenol S / epichlorohydrin type epoxy resin, bisphenol AD / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, ethylene oxide adduct of bisphenol A or epichlorohydrin type epoxy of propylene oxide adduct Resin, polyglycidyl ether of glycerin / epichlorohydrin adduct, naphthalenediol diglycidyl ether, resorcinol diglycidyl ether, polybutadiene Glycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl Ether, dihydroxybenzophenone diglycidyl ether,
Biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N
-Diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N
-Diglycidyl toluidine, JP2004-156024A, JP2004-315
Examples thereof include an epoxy compound having excellent flexibility disclosed in Japanese Patent No. 595 and Japanese Patent Application Laid-Open No. 2004-323777, and an epoxy compound having a structure represented by the above formulas (4) to (6).

Further, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, “Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd.
, "Epicoat 1032H60", "Epicoat 604", "Epicoat 630",
Phenol novolac epoxy resin, cresol novolac epoxy resin,
Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, ethylene glycol / epichlorohydrin adduct polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

In particular, when an isocyanurate ring-containing epoxy compound such as trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate is used in the present invention, the adhesive strength tends to be improved with respect to polyimide or copper. ,preferable. In addition, “Epicoat 1031S” and “Epicoat 1032H60” manufactured by Japan Epoxy Resin Co., Ltd.
, "Epicoat 604", and "Epicoat 630" are highly functional in the present invention because they are multifunctional and have excellent heat resistance.
04-156024, JP-A 2004-315595, JP-A 2004-323
The epoxy compound described in Japanese Patent No. 777 is preferable because the cured coating film is excellent in flexibility. Further, a dicyclopentadiene type epoxy compound described in JP-A No. 2001-240654,
In the present invention, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenol / epichlorohydrin type epoxy resin, etc. are used in the present invention for the durability of cured coatings including thermosetting, hygroscopicity and heat resistance. In terms of surface quality, it is preferable.

In the present invention, in addition to the epoxy curing agent (B), for example, a compound having one epoxy group in the molecule can be used in combination. Specifically, for example, compounds such as N-glycidyl phthalimide, glycidyl and glycidyl (meth) acrylate are preferable. By using these together, it becomes easy to control the crosslinking density of the thermally conductive insulating layer. Specific examples include compounds such as N-glycidyl phthalimide, glycidyl, and glycidyl (meth) acrylate.

In the present invention, the amount of the epoxy curing agent (B) used is an addition type polyester resin (A) 10
It is preferably added at a ratio of 0.5 to 100 parts by weight with respect to 0 part by weight, more preferably 1 to 80 parts by weight. When the amount of the curing agent (B) used is less than 0.5 parts by weight,
There is a risk that the crosslink density of the heat conductive insulating layer is insufficient, and the adhesive strength and heat resistance are insufficient. On the other hand, when the amount used is more than 100 parts by weight, the crosslink density of the heat conductive insulating layer becomes excessive, and not only the flexibility but also the adhesive strength may be lowered.

In the present invention, the thermally conductive insulating reliable filler (C) is a compound that imparts thermal conductivity to the thermally conductive insulating layer. Specifically, the heat conductive insulating reliability filler (C) is aluminum hydroxide,
Magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride and other metal oxides, metal nitrides, hydrated metal compounds, crystalline silica, amorphous silica Silicon carbide and the like are preferable. Among these, aluminum oxide, aluminum nitride, and boron nitride are more preferable, and aluminum oxide is particularly preferable from the viewpoints of heat resistance and insulation reliability. Spherical aluminum oxide is excellent in that it can be closely packed in the heat conductive insulating layer, and is most preferable in that the increase in the elastic modulus of the resin composition is small even when a large amount is added.

The particle size of the thermally conductive insulating reliable filler (C) is usually preferably 0.1 to 250 μm, 0
. 5-100 micrometers is more preferable. The particle shape may be any shape such as a spherical shape, a needle shape, a flake shape, or a dendritic shape. The average particle diameter of the thermally conductive insulating reliable filler can be obtained by measurement by a general laser diffraction method, scattering method, etc., and the average diameter when assuming a circle equal to the projected area of the fine particle aggregate The value is the average particle size.

The heat conductive insulating reliability filler (C) is a ratio of 30 to 130 with respect to the addition type polyester resin (A) 100 by volume ratio, or with respect to the addition type polyester resin (A) 100 by weight ratio, It is preferable to use it in the ratio of 12-520. When the heat conductive insulating reliability filler (C) is used in the above volume ratio or weight ratio range, the heat conductivity of the heat conductive adhesive sheet is 0.5 W / m.
・ It can be over k. On the other hand, if the ratio is small when used outside the range, the desired thermal conductivity may not be obtained. Moreover, when there are too many ratios used, there exists a possibility that an adhesive characteristic and insulation reliability may fall. In order to dissipate heat from the electronic component, a thermal conductivity of 0.5 W / m · k or more is preferable.

A coupling agent can also be mix | blended with the heat conductive insulating resin composition of this invention for adhesiveness improvement. Moreover, aluminum hydroxide and magnesium hydroxide can be blended for imparting flame retardancy. Moreover, the insulation reliability at the time of moisture absorption can be improved by mix | blending an ion supplement agent. Moreover, a leveling agent etc. can be mix | blended.

In the heat conductive insulating resin composition of the present invention, it is preferable to add a solvent in order to uniformly disperse the heat conductive insulating reliability filler (C) in the composition.

The solvent is a relatively low boiling point methyl ethyl ketone, acetone, methyl isobutyl ketone, 2-ethoxyethanol, toluene, butyl cellosolve, methanol, ethanol,
2-methoxyethanol and the like are preferable. Further, a high boiling point solvent may be added in order to adjust the drying speed during coating. As the high boiling point solvent, dimethylacetamide, dimethylformamide, methylpyrrolidone, and cyclohexanone are preferable.

The heat conductive insulating resin composition comprises an addition type polyester resin (A) and an epoxy curing agent (B).
And it is preferable to manufacture by thermally mixing the thermally conductive insulating filler (C) and the solvent.

For stirring and mixing, for example, scandex, paint conditioner, sand mill,
These can be carried out using a raking machine, a three-roller and a bead mill, or a combination thereof. Furthermore, vacuum defoaming is preferably performed in order to remove bubbles from the thermally conductive insulating resin composition after stirring and mixing.

The heat conductive adhesive sheet of this invention is a sheet | seat which has a heat conductive insulating layer formed by coating and drying a heat conductive insulating resin composition on a base material. In addition, a heat conductive adhesive sheet may be called a heat conductive film etc.

As a coating method, a known knife coat, die coat, lip coat, roll coat, curtain coat, bar coat, gravure coat, flexo coat, dip coat, spray coat, spin coat and the like can be used.

As the substrate, a plastic film such as a polyester film, a polyethylene film, a polypropylene film, or a polyimide film, a film subjected to a release treatment (hereinafter also referred to as a release film), or the like can be used. Furthermore, metals such as aluminum, copper, stainless steel, and beryllium copper, and foils of these alloys can be used as a substrate.

The thickness of the thermally conductive insulating layer can be determined as appropriate, but from the viewpoint of adhesive properties and thermal conductivity,
The thickness is usually 10 to 200 μm, preferably 30 to 150 μm.

It is preferable to use the heat conductive adhesive sheet of this invention as a sheet | seat which affixes the electronic component and heat radiating member which are heat dissipation objects. As a method of use, the two can be strongly adhered by pressure bonding and heating.

Examples of the electronic components include LED substrates, IC chips, hybrid packages, multi-modules, power transistors, plastics, integrated circuits, and the like.

Examples of the heat radiating member include a heat sink made of a metal foil or sheet such as aluminum or copper as a material for forming a heat conductive substrate, and other heat radiators.

The heat conductive insulating resin composition and the heat conductive adhesive sheet of the present invention can be widely used not only for bonding the electronic component and the heat radiating member, but also for bonding heat radiating members such as building materials, vehicles, aircrafts and ships. .

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, and Mw means a weight average molecular weight.

<Measurement of weight average molecular weight (Mw)>
Mw is measured by GPC (Gel Permeation Chromatography) “H” manufactured by Tosoh Corporation.
PC-8020 "was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, two columns “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) are connected in series, and the flow rate is 0.6 ml / mi.
n, The column temperature was 40 ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene.

[Synthesis Example 1]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, polycarbonate diol (Kuraray polyol C-2090: Kuraray Co., Ltd .: 3-methyl-
Copolymerized polycarbonate diol of 1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio): hydroxyl value = 56 mg KOH / g, Mw = 2000) 292.1 parts for main chain 44.9 parts of tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) as an acid anhydride group-containing compound, 350 parts of toluene as a solvent,
While stirring, the temperature was raised to 60 ° C. and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., bisphenol A type epoxy resin (
YD-8125: manufactured by Tohto Kasei Co., Ltd .: epoxy equivalent = 175 g / eq) 62.9 parts, 4 parts of triphenylphosphine as a catalyst were added, the temperature was raised to 110 ° C., and the reaction was performed for 8 hours.
10. After cooling to room temperature, tetrahydrophthalic anhydride as an acid anhydride group-containing compound for the side chain
8 parts were added and reacted at 110 ° C. for 3 hours. After cooling to room temperature, the nonvolatile content is 3 with toluene
The polyester resin solution was obtained by adjusting to 5%. The weight average molecular weight of the addition-type polyester resin (A) obtained by this synthesis example is 12600, and the acid value of the resin non-volatile content measured is 1
It was 5.3 mgKOH / g.

[Synthesis Examples 2 to 29, Comparative Synthesis Examples 1 to 7]
A polyester resin was obtained by synthesizing in the same manner as in Synthesis Example 1 except that the raw materials of the synthesis examples were replaced with the raw materials described in Tables 1 to 3.

The molar ratio in the table indicates the functional group ratio of each raw material when the hydroxyl group of the polyol compound (a) is 1 mol.

C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymer polycarbonate polyol (weight average molecular weight about 2000)
T-5562: Asahi Kasei Chemicals Corporation: C ₅ C ₆ copolymer polycarbonate diol (
Number average molecular weight about 2000)
UHC50-200: Ube Industries, Ltd .: 1,6-hexanediol / caprolactone = 5/5 copolymer polycarbonate polyol (weight average molecular weight about 2000)
UC-100: manufactured by Ube Industries, Ltd .: 1,4-cyclohexanedimethanol base polycarbonate polyol weight average molecular weight of about 1000)
PTG-2000SN: Hodogaya Chemical Co., Ltd .: Polytetramethylene glycol (number average molecular weight of about 2000)
PTG-L2000: Hodogaya Chemical Co., Ltd .: Polytetramethylene glycol (weight average molecular weight about 2000)
GI-2000: Nippon Soda Co., Ltd .: Hydrogenated polybutadiene glycol (weight average molecular weight of about 2100)
G-2000: Nippon Soda Co., Ltd .: α, ω-polybutadiene glycol (weight average molecular weight about 1800)
Poly-ip: manufactured by Idemitsu Kosan Co., Ltd .: hydroxyl-terminated liquid isoprene (weight average molecular weight of about 2)
500)
KF-6002: Shin-Etsu Chemical Co., Ltd .: Both ends carbinol-modified silicone oil (weight average molecular weight about 3000)
P-1041: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol (weight average molecular weight of about 1000)
P-2041: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol (weight average molecular weight of about 2000)
P-2010: Kuraray Co., Ltd .: Aliphatic polyester polyol (weight average molecular weight of about 2
000)
C-590: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymer polycarbonate polyol (weight average molecular weight of about 6)
00)
TH: Shin Nippon Rika Co., Ltd .: Tetrahydrophthalic anhydride HNA-100: Shin Nippon Rika Co., Ltd .: Methylbicyclo [2.2.1] heptane-2,
3-dicarboxylic anhydride anhydrous TMA: trimellitic anhydride SA: manufactured by Nippon Nippon Chemical Co., Ltd .: succinic anhydride YD-8125: manufactured by Tohto Kasei Co., Ltd .: bisphenol A type epoxy resin EX-216L: manufactured by Nagase ChemteX Corporation : Cyclohexane dimethanol diglycidyl ether EX-214L: manufactured by Nagase ChemteX Corporation: 1,4-butanediol-diglycidyl ether EX-212L: manufactured by Nagase ChemteX Corporation: 1,6-hexanediol diglycidyl ether BHPA: N, N-bis (2-hydroxypropyl) aniline DMBA: dimethylolbutanoic acid TMP: trimethylolpropane

Example 1
For 100 parts of the nonvolatile content of the addition type polyester resin (A) solution obtained in Synthesis Example 1,
As a heat conductive insulating reliable filler, 600 parts of alumina (manufactured by Admatech Co., Ltd., AO-509) having an average particle diameter of 10 μm was added. To this, 3 mm glass beads (manufactured by Potters Ballotini Co., Ltd., GB603M) were added, and methyl ethyl ketone was further added to adjust the viscosity, and the mixture was dispersed for 3 hours with a paint conditioner. And the obtained dispersion was made into a polyfunctional glycidyl ether type epoxy resin (Japan Epoxy Resin Co., Ltd., EP1031).
S) A thermally conductive insulating resin composition was obtained by adding 20 parts. The obtained thermally conductive insulating resin composition was applied to a release treatment sheet (a release treatment polyethylene terephthalate film having a thickness of 75 μm) using a comma coater, and heated and dried at 100 ° C. for 2 minutes. Dry film thickness is 65
A μm heat conductive adhesive sheet was prepared.

(Examples 2-29)
Except having changed the polyester resin solution into the synthesis examples 2-29, respectively, it carried out similarly to Example 1 and created the heat conductive adhesive sheet.

(Examples 30 to 38, Comparative Examples 1 to 7)
Except having changed the raw material of Example 1 into the raw material described in Table 4 or Table 5, it carried out similarly to Example 1 and created the heat conductive adhesive sheet.

EP1031S: Made by Japan Epoxy Resin Co., Ltd .: Multifunctional glycidyl ether type epoxy resin AO-509: Made by Admatech Co., Ltd .: Aluminum oxide (average particle size: 10 μm)
H grade: Tokuyama Co., Ltd .: Aluminum nitride (average particle size: 1.1 μm)
PT160: Momentive Performance Material Co., Ltd .: Boron nitride (average particle size: 16 μm)
Pyroxuma 5301: Kyowa Chemical Co., Ltd .: Magnesium oxide (average particle size: 2 μm)
1 type of zinc oxide: manufactured by Hakusuitec Co., Ltd .: zinc oxide (average particle size: 0.5 μm)
1110: Mitsui Kinzoku Co., Ltd .: Copper powder E-1011: Tosoh-Silica Co., Ltd .: Silica Examples and comparative examples, heat conductive adhesive sheets obtained with adhesive strength, solder bath resistance, humidified solder bath Resistance, insulation reliability, and heat conduction characteristics were evaluated by the following methods.

(1) Adhesive strength A two-layer CCL made of copper and polyimide (Sumitomo Metal Mining Co., Ltd., S524-38E) is peeled off from a thermally conductive adhesive sheet having a width of 25 mm and a length of 110 mm.
21) was sandwiched between the polyimide surface and the aluminum plate and subjected to pressure bonding for 1 hour under the conditions of 150 ° C. and 2.0 MPA to prepare an evaluation test piece. The test specimen for evaluation was subjected to a T-peel peeling test under an atmosphere of 25 ° C. and 50% relative humidity at a pulling speed of 300 mm / min, and the adhesive strength (N / c
m) was measured. This test evaluates the adhesive strength of the adhesive layer when used at room temperature, and the results were judged according to the following criteria.
◎ ・ ・ ・ "6 (N / cm) <Adhesive strength"
○ "4 (N / cm) <Adhesive strength ≤ 6 (N / cm)"
Δ: “2 (N / cm) <Adhesive strength ≦ 4 (N / cm)”
X ... "Adhesive strength ≤ 2 (N / cm)"

(2) Solder bath resistance A test piece was prepared in the same manner as in (1) above, and the aluminum plate surface was brought into contact with 260 ° C. molten solder and floated for 1 minute. Then, visually observe the appearance of the test piece, foaming and floating of the heat conductive insulating layer,
The presence or absence of adhesion abnormality such as peeling was evaluated. This test evaluates the thermal stability of the thermally conductive insulating layer at the time of solder contact with the appearance. The one with good heat resistance has no change in appearance before and after the soldering process. Inferior properties cause foaming and peeling after soldering. These evaluation results were judged according to the following criteria.
◎ ・ ・ ・ No change in appearance
○ ・ ・ ・ “Slight foaming is observed”
△ ... "Bubbling is observed"
× ・ ・ ・ "Strong foaming and peeling are observed"

(3) Humidity solder bath resistance A test piece was prepared in the same manner as in (1) above, and left to humidify in an atmosphere of 40 ° C. and 90% relative humidity for 72 hours. And left floating for 1 minute. Thereafter, the appearance of the test piece was visually observed to evaluate the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the heat conductive insulating layer. This test is to evaluate the thermal stability of the heat conductive insulating layer at the time of solder contact in a humidified state by appearance, while those having good heat and moisture resistance do not change the appearance, For those with poor heat and humidity resistance, foaming and peeling occur after soldering. These evaluation results were judged according to the following criteria.
◎ ・ ・ ・ “No change in appearance”
○ ・ ・ ・ “Almost no change in appearance”
△ ... "Bubbling is observed"
× ・ ・ ・ "Strong foaming and peeling are observed"

(4) Peel off the release treatment sheet from the thermally conductive adhesive sheet having a size of insulation reliability width 65 mm × length 65 mm,
Polyimide film with a thickness of 25 μm [“Kapton 100H” manufactured by Toray DuPont Co., Ltd.]
Comb pattern (copper pattern width / space width = 50) in which a copper circuit is formed on polyimide.
(μm / 50 μm) was sandwiched between printed circuit boards and subjected to pressure bonding treatment at 150 ° C. and 2.0 MPA for 1 hour to prepare test pieces for evaluation. A DC voltage of 50 V was continuously applied to the copper circuit of the test piece for 100 hours under an atmosphere of 130 ° C. and 85% relative humidity, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are as follows.
◎ ・ ・ ・ Insulation resistance value 10 ⁸ Ω or more ○ ・ ・ ・ Insulation resistance value 10 ⁷ or more and less than 10 ⁸ Ω △ ・ ・ ・ Insulation resistance value 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・ Insulation resistance value less than 10 ⁶ Ω

(5) Thermal conductive property A thermal conductive adhesive sheet having a size of 65 mm × 65 mm is 1 at 150 ° C. and 2.0 MPa.
A time pressing process was performed to prepare a test piece for evaluation. Thereafter, the release treatment sheet is peeled off and the width 1
A test piece of 0 mm × 10 mm in length was cut out, and the thermal diffusivity was measured with a periodic heating method thermal diffusivity measuring apparatus (FTC-1 manufactured by ULVAC-RIKO) in an atmosphere of 25 ° C. and 50% relative humidity. Also,
The density of the heat conductive sheet subjected to pressure-bonding treatment for 1 hour under the conditions of 150 ° C. and 2.0 MPA was measured by an underwater substitution method. Furthermore, the specific heat capacity of the test piece was measured with a differential scanning calorimeter DSC 6220 (manufactured by SII Nanotechnology Inc.). And the heat conductivity of the test piece for evaluation was computed from the data of the thermal diffusivity, density, and specific heat capacity of the sample. The evaluation criteria are as follows.
◎ ... Thermal conductivity 1.0 W / m · k or more ○… Thermal conductivity 0.5 or more and less than 1.0 W / m · k Δ… Thermal conductivity 0.2 or more 0.5 W / m・ Less than k × ・ ・ ・ Heat conductivity less than 0.2 W / m · k

As is apparent from Table 6, Examples 1 to 38 of the present invention satisfy all the adhesive properties, solder heat resistance, and insulation reliability.

On the other hand, since Comparative Examples 1 to 5 do not use the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring in the main chain of the addition-type polyester resin, insulation reliability, solder heat resistance, Adhesive properties deteriorated significantly. In Comparative Example 6, since the heat conductive insulating filler (C) uses copper powder that does not have insulation reliability, the insulation reliability, solder heat resistance, and adhesive properties are good, but the insulation reliability There is no sex. Further, since Comparative Example 7 uses silica that is not a thermally conductive insulating filler, the solder heat resistance and the insulation reliability are good, but the adhesion characteristics and the heat conduction characteristics are remarkably deteriorated.

Claims (5)

The addition type polyester resin (A-1) and the compound (c) having two or more epoxy groups are reacted to obtain an addition type polyester resin (A-2).
The addition-type polyester resin (A-3) having a cyclic structure in the main chain by reacting the addition-type polyester resin (A-2) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. )
Furthermore, the heat conductive insulation which stirs and mixes the addition type polyester resin (A-3), the epoxy curing agent (B) containing two or more epoxy groups in the molecule, and the heat conductive insulating filler (C). A method for producing a resin composition. The thermal conductivity according to claim 1, wherein the polyol compound (a) is reacted with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring to obtain an addition type polyester resin (A-1). A method for producing an insulating resin composition. The manufacturing method of the heat conductive insulating resin composition of Claim 1 or 2 whose acid value of addition-type polyester resin (A-3) is 1-100 mgKOH / g. The manufacturing method of the heat conductive insulating resin composition of any one of Claims 1-3 whose weight average molecular weights of addition type polyester resin (A-3) are 5000-500000. The addition type polyester resin (A-1) and the compound (c) having two or more epoxy groups are reacted to obtain an addition type polyester resin (A-2).
The addition-type polyester resin (A-3) having a cyclic structure in the main chain by reacting the addition-type polyester resin (A-2) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. )
Furthermore, the addition type polyester resin (A-3), the epoxy curing agent (B) containing two or more epoxy groups in the molecule, and the heat conductive insulating filler (C) are mixed by stirring and thermally conductive. An insulating resin composition;
The manufacturing method of the heat conductive adhesive sheet which forms a heat conductive insulating resin layer with the said heat conductive insulating resin composition.