JP6222428B2 - Epoxy resin composition - Google Patents

Description

The present invention relates to an adhesive epoxy resin composition, a film for forming an interlayer insulating film made of the adhesive epoxy resin composition, a wiring board provided with an interlayer insulating film made of the adhesive epoxy resin composition, and the adhesive property The present invention relates to an electronic circuit board provided with a heat dissipation member made of an epoxy resin composition.

Generally, an epoxy resin composition containing an epoxy resin and a curing agent is cured to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Can do. Therefore, epoxy resin compositions are used in a wide range of applications such as adhesives, paints, insulating materials, molding materials, casting materials, heat dissipation materials, and the like.
When using an epoxy resin composition for the above-mentioned use, it is requested | required that the viscosity of an epoxy resin composition should be made low from a viewpoint of ensuring workability | operativity.

However, when a reactive diluent is added to the epoxy resin composition, the viscosity of the epoxy resin composition can be lowered, but the adhesiveness is reduced when the epoxy resin composition is used as an adhesive. was there. Therefore, in the epoxy resin composition, there is a problem that it is difficult to ensure adhesiveness when the viscosity is reduced by adding a reactive diluent to the request to reduce the viscosity, It has been difficult to achieve both low viscosity and good adhesion.

As an epoxy resin composition having a low viscosity and excellent adhesion when cured, Patent Document 1 contains, for example, a phenol novolac type epoxy resin, a trifunctional type epoxy resin, and an amino compound. A heat resistant epoxy adhesive composition has been proposed. Patent Document 2 discloses an adhesive containing a trifunctional (meth) acrylate, a bisphenol-type epoxy (meth) acrylate having a hydroxyl group, a di (meth) acrylate having a specific structural unit, and a photopolymerization initiator. Radiation curable resin compositions have been proposed.
However, the hardened | cured material obtained by hardening the epoxy resin composition described in patent document 1, 2 had the subject that the adhesiveness with respect to a metal was not yet enough.

Japanese Patent Laid-Open No. 9-100457 JP 2006-16434 A

An object of the present invention is to provide an adhesive epoxy resin composition having a low viscosity and excellent properties of tensile shear adhesiveness and peel adhesiveness with metal when cured. .
Moreover, this invention aims at providing the wiring board provided with the film for interlayer insulation film formation which consists of an adhesive epoxy resin composition of this invention, and the interlayer insulation film which consists of the said adhesive epoxy resin composition. To do.
Furthermore, an object of this invention is to provide the electronic circuit board provided with the heat radiating member which consists of an adhesive epoxy resin composition of this invention.

As a result of intensive studies, the present inventors have (b) a specific structure (trifunctional structure having a trimethylolalkane skeleton) as a reactive diluent in addition to (a) an epoxy resin and (c) a curing agent. In the case of an epoxy resin composition containing a reactive diluent mainly composed of an epoxy compound having a low viscosity due to the inclusion of the reactive diluent, a metal is obtained when the cured product is used. It has been found that it has a characteristic that it is excellent in tensile shear adhesiveness and peel adhesiveness.
Based on these findings, the present inventors have completed the adhesive epoxy resin composition of the present invention, the interlayer insulating film forming film of the present invention, the wiring board of the present invention, and the electronic circuit board of the present invention. .

That is, the adhesive epoxy resin composition of the present invention comprises (a) an epoxy resin, (b) a reactive diluent mainly composed of an epoxy compound represented by the following general formula (1), and (c) curing. It contains an agent.

（ただし、Ｒ^１〜Ｒ^４は、炭素数１〜１０のアルキレン基、炭素数２〜１０のアルケニレン基、又は、炭素数６〜１０のアリーレン基を表し、互いに同一であっても良く、異なっていても良い。また、Ｒ^５は、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１０のアリール基、又は、水素原子を表す。）

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.)

In the adhesive epoxy resin composition of the present invention, the content of (b) reactive diluent is 5 to 95% by weight with respect to the total amount of (a) epoxy resin and (b) reactive diluent. It is preferable.

In the adhesive epoxy resin composition of the present invention, the reactive diluent (b) is preferably a reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether. In this case, (b1) The reactive diluent preferably has an epoxy equivalent of 101 to 120 g / eq, a total halogen content of 100 ppm or less, and a viscosity of 50 to 130 mPa · s.

In the adhesive epoxy resin composition of the present invention, (a) the epoxy resin is biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetra Phenylethane type epoxy resin, dicyclopentadiene phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol phenol co-condensed novolac type epoxy resin, naphthol cresol co-condensed novolac type epoxy Resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl novolac type epoxy resin, ethylphenol novolak type epoxy resin Xylene resin, butylphenol novolac type epoxy resin, octylphenol novolac type epoxy resin, xylylene skeleton-containing phenol novolac type epoxy resin, fluorene skeleton containing phenol novolac type epoxy resin, 4,4'-biphenylphenol type epoxy resin, tetramethyl-4,4 '-Biphenol type epoxy resin, dimethyl-4,4'-biphenylphenol type epoxy resin, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis (4-hydroxyphenyl) ethyl) phenyl] Propane type epoxy resin, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) type epoxy resin, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) type epoxy resin, trishydroxy Phenylmethane type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, pyrogallol type epoxy resin, diisopropylidene type epoxy resin, 1,1-di-4-hydroxyphenylfluorene type epoxy resin, phenolized polybutadiene type epoxy resin, 3,4-epoxycyclohexylmethyl-3 ′, 4′-cyclohexylcarboxylate type epoxy resin, 1,4-butanediol type epoxy resin, 1,6-hexanediol type epoxy resin, polyethylene glycol type epoxy resin, polypropylene glycol type Epoxy resin, pentaerythritol type epoxy resin, xylylene glycol derivative type epoxy resin, isocyanuric ring type epoxy resin, hydantoin ring type epoxy resin, hexahydrophthalic acid di Glycidyl ester type epoxy resin, tetrahydrophthalic acid diglycidyl ester type epoxy resin, aniline type epoxy resin, toluidine type epoxy resin, p-phenylenediamine type epoxy resin, m-phenylenediamine type epoxy resin, diaminodiphenylmethane derivative type epoxy resin, diamino It is preferably at least one selected from methylbenzene derivative type epoxy resin, brominated phenol novolac type epoxy resin, and brominated cresol novolak type epoxy resin.

In the adhesive epoxy resin composition of the present invention, (c) the curing agent is 2-ethyl-4-methylimidazole, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, trifluoride. Boron-amine complex, guanidine derivative, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified pheno Resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, polyhydric phenol novolac resins synthesized from polyvalent hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylol methane resins, tetraphenylol ethane resins, naphthol novolac resins, At least one selected from the group consisting of naphtholphenol co-condensed novolak resins, naphthol cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and alkoxy group-containing aromatic ring-modified novolak resins. Preferably there is.

The adhesive epoxy resin composition of the present invention preferably further contains (d) a filler, and (d) the filler is preferably boron nitride.

The adhesive epoxy resin composition of the present invention is preferably used for forming an interlayer insulating film or a heat dissipation member provided on an electronic circuit board.

The film for forming an interlayer insulating film of the present invention is characterized by comprising the adhesive epoxy resin composition of the present invention.

The wiring board of the present invention includes an interlayer insulating film made of the adhesive epoxy resin composition of the present invention.

The electronic circuit board of the present invention is characterized by including a heat dissipating member made of an adhesive epoxy resin composition containing the filler (d) of the present invention.

The adhesive epoxy resin composition of the present invention includes a reactive diluent mainly composed of an epoxy compound having (b) a specific structure (trifunctional structure having a trimethylolalkane skeleton), so that the viscosity is low. When it is made into a cured product, it has a characteristic that it has excellent tensile shear adhesive strength and peel adhesive strength with metal.
In addition, since (b) a reactive diluent containing an epoxy compound having a specific structure as a main component is included, (d) the tensile shear bond strength with a metal and a cured product even when containing a filler and It has the property that it has excellent peel adhesive strength, and (d) the filler can be uniformly dispersed in the adhesive epoxy resin composition.
Therefore, the adhesive epoxy resin composition of the present invention can be very suitably used for forming an interlayer insulating film or a heat dissipation member provided on an electronic circuit board.

The film for forming an interlayer insulating film of the present invention is composed of the adhesive epoxy resin composition of the present invention which is excellent in tensile shear adhesive strength and peel adhesive strength with a metal when used as an interlayer insulating film. An interlayer insulating film excellent in adhesion can be provided.
Moreover, since the wiring board of the present invention includes the interlayer insulating film made of the adhesive epoxy resin composition of the present invention, the metal circuit and the interlayer insulating film have high adhesion, and the occurrence of peeling of the metal circuit is avoided. Can be excellent in reliability.
Moreover, since the electronic circuit board of this invention is equipped with the heat radiating member which consists of an adhesive epoxy resin composition containing the (d) filler of this invention, it was excellent adhesion between metal members, such as a circuit, and a heat radiating member. And sufficient heat dissipation can be ensured.

<< Adhesive Epoxy Resin Composition >>
First, the adhesive epoxy resin composition of the present invention will be described.
The adhesive epoxy resin composition of the present invention comprises (a) an epoxy resin, (b) a reactive diluent mainly comprising an epoxy compound having a specific structure (trifunctional structure having a trimethylolalkane skeleton), and (C) It contains a curing agent.

<(B) Reactive diluent>
The (b) reactive diluent is a reactive diluent mainly composed of an epoxy compound represented by the following general formula (1).

（ただし、Ｒ^１〜Ｒ^４は、炭素数１〜１０のアルキレン基、炭素数２〜１０のアルケニレン基、又は、炭素数６〜１０のアリーレン基を表し、互いに同一であっても良く、異なっていても良い。また、Ｒ^５は、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１０のアリール基、又は、水素原子を表す。）

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.)

In the adhesive epoxy resin composition of the present invention, it is very important to use a reactive diluent mainly composed of the epoxy compound represented by the general formula (1) as the reactive diluent (b). . The adhesive epoxy resin composition of the present invention has a low viscosity because it contains a reactive diluent mainly composed of an epoxy compound having such a specific structure (trifunctional structure having a trimethylolalkane skeleton). However, when it is made into a cured product, it has the property of being excellent in tensile shear adhesive strength and peel adhesive strength with metal, and these excellent adhesive strengths are maintained even when (d) a filler is contained. be able to.
Moreover, since it has these characteristics, it can be used very suitably for forming an interlayer insulation film, a heat radiating member provided in an electronic circuit board, etc.

In the present invention, “having the epoxy compound represented by the general formula (1) as a main component” means that the epoxy compound represented by the general formula (1) is 50 wt% in the reactive diluent (b). This includes the above.

R < ¹ > -R < ⁴ > in the said General formula (1) represents a C1-C10 alkylene group, a C2-C10 alkenylene group, or a C6-C10 arylene group.
The alkylene group having 1 to 10 carbon atoms or the alkenylene group having 2 to 10 carbon atoms may be linear or branched. Moreover, the skeleton of the arylene group having 6 to 10 carbon atoms may have a monocyclic structure or a condensed ring structure.
All or part of the hydrogen atoms contained in R ^{1 to} R ⁴ may be substituted.
R ^{1 to} R ⁴ may be the same as or different from each other.

R ⁵ in the general formula (1) represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.
The alkyl group having 1 to 10 carbon atoms or the alkenyl group having 2 to 10 carbon atoms may be linear or branched. Further, the aryl group having 6 to 10 carbon atoms may have a skeleton having a monocyclic structure or a condensed ring structure.
All or part of the hydrogen atoms contained in R ⁵ may be substituted.

The epoxy compound represented by the general formula (1) contained as a main component in the (b) reactive diluent is not particularly limited as long as it is represented by the general formula (1). , Trimethylolpropane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, and the like.
The epoxy compound represented by the general formula (1) contained as a main component in the reactive diluent (b) may be used alone or in combination of two or more.

The reactive diluent (b) is preferably a reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether. When the reactive diluent (b1) containing trimethylolpropane triglycidyl ether as a main component is used, the tensile shear bond strength and peel bond strength with a metal are excellent when cured as a cured product while having low viscosity. And the effect that the adhesiveness of the cured product can be maintained even when (d) a filler is contained. The reason is presumed that trimethylolpropane triglycidyl ether has a trifunctional structure having a trimethylolalkane skeleton and a specific tetrahedral skeleton.
The chemical structural formula of trimethylolpropane triglycidyl ether is shown in the following formula (2).

In the case where the reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether is used as the reactive diluent (b), the concentration of trimethylolpropane triglycidyl ether in the reactive diluent (b1) (In the present invention, corresponding to the purity of trimethylolpropane triglycidyl ether) is very important.
The reason for this is that in the synthesis of trimethylolpropane triglycidyl ether, when the alcoholic hydroxyl group of trimethylolpropane is glycidyl etherified, the raw material compound remains unreacted, or a bifunctional structure, monofunctional structure, oligomer, etc. When these impurities are present in a large amount (when the purity of trimethylolpropane triglycidyl ether is low), a trifunctional structure having a trimethylolalkane skeleton or a specific tetrahedron This is because the above-described effects resulting from the skeleton may not be enjoyed.

Examples of the purity index of trimethylolpropane triglycidyl ether in the reactive diluent (b1) include the epoxy equivalent, the total halogen content and the viscosity of the reactive diluent (b1).
The epoxy equivalent of the reactive diluent (b1) has a theoretical value of about 101 g / eq, assuming that the purity of the trimethylolpropane triglycidyl ether in the reactive diluent (b1) is 100%. The greater the amount of impurities such as bifunctional structure, monofunctional structure and unreacted material contained in the agent (b1), that is, the purity of trimethylolpropane triglycidyl ether in the reactive diluent (b1) The lower the value is, the higher the actual measurement value is than the theoretical value. Therefore, it can be said that the purity of the trimethylolpropane triglycidyl ether in the reactive diluent (b1) is higher as the measured value of the epoxy equivalent of the reactive diluent (b1) is closer to the theoretical value.

Moreover, about the viscosity of a reactive diluent (b1), when the oligomer is contained as an impurity in the reactive diluent (b1), there exists a tendency for a viscosity to become high, Therefore The viscosity of a reactive diluent (b1) The lower the value, the higher the purity of trimethylolpropane triglycidyl ether in the reactive diluent (b1).

The total amount of halogen in the reactive diluent (b1) is determined when glycidyl etherification is carried out by reacting trimethylolpropane with epihalohydrin when the alcoholic hydroxyl group of trimethylolpropane is glycidyl etherified. Is reactive because the unreacted epihalohydrin remains as an impurity, and as a result, the total halogen content in the reactive diluent (b1) increases and the content of trimethylolpropane triglycidyl ether decreases relatively. The relationship is established that the smaller the total halogen content of the diluent (b1), the higher the purity of trimethylolpropane triglycidyl ether in the reactive diluent (b1).
When epichlorohydrin is used as the epihalohydrin, the amount of chlorine is increased, when epibromohydrin is used, the amount of bromine is increased, and when epiiohydrin is used, the amount of iodine is increased. This is because the amount of fluorine increases when epifluorohydrin is used.

In the case where the reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether is used as the reactive diluent (b), the epoxy equivalent of the reactive diluent (b1) is 90 to 200 g / eq. It is preferable that it is 101-120 g / eq.
This is because when the epoxy equivalent is within this range, the tensile shear adhesive strength and peel adhesive strength with a metal are particularly good when cured.
Moreover, when the epoxy equivalent is in the above range, when the filler (d) is blended in the adhesive epoxy resin composition, good adhesion between the cured epoxy component and the filler (d) is obtained. Can be secured.

In the case where the reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether is used as the reactive diluent (b), the total halogen content of the reactive diluent (b1) is 100000 ppm or less. Is more preferable, and 100 ppm or less is more preferable.
This is because when the total halogen content is within this range, the tensile shear bond strength and peel bond strength with the metal are particularly good when cured.
In addition, when the total halogen content is in the above range, when (d) filler is blended in the adhesive epoxy resin composition, good adhesion between the cured epoxy component and (d) filler. Can be secured.
If the total halogen content exceeds 100,000 ppm, the electrical insulation of the cured product may be reduced when the adhesive epoxy resin composition containing the reactive diluent (b1) is used for an interlayer insulating film. Occurs.

When trimethylolpropane triglycidyl ether is synthesized by reacting trimethylolpropane with epihalohydrin, epichlorohydrin is generally used as the epihalohydrin. Therefore, in this invention, it is preferable that the total chlorine amount in a reactive diluent (b1) is 100000 ppm or less, and it is more preferable that it is 100 ppm or less.

In the present invention, the total halogen content in the reactive diluent (b1) is determined by the following method.
That is, the total amount of chlorine in the reactive diluent (b1) is based on JIS K 7243-3, the total amount of bromine is based on JIS K 7392, the amount of iodine is based on JIS K 6217-1, The amount is measured according to JIS K 0102 34.1, and the value obtained by adding the respective measured values is defined as the total halogen amount.

When the reactive diluent (b1) mainly composed of trimethylolpropane triglycidyl ether is used as the reactive diluent (b), the reactive diluent (b1) has a viscosity of 10 to 500 mPa · s. It is preferable that the viscosity is 50 to 130 mPa · s. The reason is that when the viscosity is within this range, the tensile shear bond strength and peel bond strength with the metal are particularly excellent when the cured product is used.
Moreover, when the viscosity is in the above range, when (d) filler is blended in the adhesive epoxy resin composition, good adhesion between the cured epoxy component and (d) filler is ensured. can do.
In addition, in this invention, a viscosity means the viscosity in 25 degreeC.

The content of the (b) reactive diluent is not particularly limited, but is preferably 5 to 95% by weight based on the total amount of the (a) epoxy resin and the (b) reactive diluent, It is more preferably 5 to 70% by weight, and further preferably 5 to 50% by weight. When the content of the reactive diluent (b) is less than 5% by weight, the viscosity of the epoxy resin composition may increase, and when it exceeds 95% by weight, the mechanical properties of the cured product may decrease. is there.

<(A) Epoxy resin>
In the present invention, the above (a) epoxy resin refers to a resin (compound) having an epoxy group, which does not correspond to the above (b) reactive diluent.
The (a) epoxy resin is not particularly limited, and a known epoxy resin can be used. Specific examples thereof include, for example, a biphenyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, a phenol novolac type epoxy resin, and cresol. Novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol phenol Condensed novolac type epoxy resin, naphthol cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl novolac Type epoxy resin, ethylphenol novolak type epoxy resin, butylphenol novolak type epoxy resin, octylphenol novolak type epoxy resin, xylylene skeleton containing phenol novolak type epoxy resin, fluorene skeleton containing phenol novolak type epoxy resin, 4,4'-biphenylphenol type epoxy Resin, tetramethyl-4,4′-biphenol type epoxy resin, dimethyl-4,4′-biphenylphenol type epoxy resin, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis (4 -Hydroxyphenyl) ethyl) phenyl] propane type epoxy resin, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) type epoxy resin, 4,4'-butylidenebis (3-methyl-6-tert-butyl) Phenol) type epoxy resin, trishydroxyphenylmethane type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, pyrogallol type epoxy resin, diisopropylidene type epoxy resin, 1,1-di-4-hydroxyphenylfluorene type epoxy resin Phenolic polybutadiene type epoxy resin, 3,4-epoxycyclohexylmethyl-3 ′, 4′-cyclohexylcarboxylate type epoxy resin, 1,4-butanediol type epoxy resin, 1,6-hexanediol type epoxy resin, polyethylene Glycol type epoxy resin, polypropylene glycol type epoxy resin, pentaerythritol type epoxy resin, xylylene glycol derivative type epoxy resin, isocyanuric ring type epoxy resin, hydantoy Ring type epoxy resin, hexahydrophthalic acid diglycidyl ester type epoxy resin, tetrahydrophthalic acid diglycidyl ester type epoxy resin, aniline type epoxy resin, toluidine type epoxy resin, p-phenylenediamine type epoxy resin, m-phenylenediamine type epoxy Resin, diaminodiphenylmethane derivative type epoxy resin, diaminomethylbenzene derivative type epoxy resin, brominated phenol novolac type epoxy resin, brominated cresol novolac type epoxy resin and the like.
These (a) epoxy resins may be used independently and may use 2 or more types together.

Although content of the said (a) epoxy resin is not specifically limited, It is preferable that it is 1 to 60 weight% in the said adhesive epoxy resin composition, and it is more preferable that it is 5 to 50 weight%. When the content of the epoxy resin (a) is less than 1% by weight, the mechanical properties of the cured product may be lowered. When the content exceeds 60% by weight, the viscosity of the epoxy resin composition is increased and the workability is inferior. Sometimes.

<(C) Curing agent>
The (c) curing agent is not particularly limited, and a known curing agent can be used. Specific examples thereof include 2-ethyl-4-methylimidazole, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, Diaminodiphenyl sulfone, isophorone diamine, imidazole, boron trifluoride-amine complex, guanidine derivative, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride , Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, polyhydric phenol novolac resin synthesized from polyhydric hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol Examples include ethane resins, naphthol novolak resins, naphthol phenol co-condensed novolak resins, naphthol cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, alkoxy group-containing aromatic ring-modified novolak resins, and the like.
These (c) curing agents may be used alone or in combination of two or more.

The phenol aralkyl resin is also referred to as a zyloc resin.
The biphenyl-modified phenol resin refers to a polyhydric phenol compound in which phenol nuclei are linked by a bismethylene group.
The biphenyl-modified naphthol resin is a polyvalent naphthol compound in which naphthol nuclei are linked by a bismethylene group.
The aminotriazine-modified phenol resin refers to a polyhydric phenol compound in which phenol nuclei are linked with melamine, benzoguanamine or the like.
The alkoxy group-containing aromatic ring-modified novolak resin refers to a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are connected with formaldehyde.

The content of the curing agent (c) may be an amount usually blended in the epoxy resin composition, and (a) the epoxy resin and (b) the reactive diluent contained in the adhesive epoxy resin composition. It may be set as appropriate in consideration of the epoxy equivalent of and the blending rules of various curing agents.

The adhesive epoxy resin composition may contain other optional components as required in addition to the (a) epoxy resin, (b) reactive diluent, and (c) curing agent.
Examples of the other optional components include (d) a filler, (e) a curing accelerator, (f) an organic solvent, and (g) an adhesion promoter.

<(D) Filler>
The (d) filler is not particularly limited, and a known filler can be used, and examples thereof include those made of inorganic oxides, inorganic salts, glass, nitrides, metal powders, and the like. The epoxy resin composition may be appropriately selected and used according to the use of the epoxy resin composition.
The inorganic oxide is not particularly limited, and examples thereof include titanium oxide, silicon oxide, aluminum oxide, beryllium oxide, and zirconium oxide.
The inorganic salt is not particularly limited, and examples thereof include calcium carbonate, barium sulfate, zirconium silicate, calcium silicate, and magnesium silicate.
The nitride is not particularly limited, and examples thereof include boron nitride, aluminum nitride, gallium nitride, indium nitride, and silicon nitride.
It does not specifically limit as said metal powder, For example, silver powder, copper powder, silver plating copper powder, tin plating copper powder, nickel powder, aluminum powder etc. are mentioned.
When the adhesive epoxy resin composition of the present invention is used to form a heat dissipation member provided on an electronic circuit board, the filler (d) is preferably boron nitride. The reason is that the thermal conductivity is high and the thermal expansion coefficient is low.
These (d) fillers may be used alone or in combination of two or more.
In addition, the shape of the filler (d) is not particularly limited, and may be any shape such as a particulate shape, a fibrous shape, and a scale shape.

When the said adhesive epoxy resin composition contains the said (d) filler, the content is although it does not specifically limit, It is preferable that it is 5-95 weight% in the said adhesive epoxy resin composition. More preferably, it is -80 weight%.
When the content of the filler (d) is less than 5% by weight, the thermal expansion coefficient may be high, and when it exceeds 95% by weight, the viscosity may be high and workability may be reduced.

<(E) Curing accelerator>
In the present invention, the above (e) curing accelerator refers to a substance that does not crosslink itself when the adhesive epoxy resin composition is cured, but promotes a crosslinking reaction.
The (e) curing accelerator is not particularly limited, and a known curing accelerator can be used. Examples thereof include triphenylphosphine, imidazole, and tertiary amine.
The imidazole is not particularly limited. For example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methyl Examples include imidazole.
The tertiary amine is not particularly limited, and for example, benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine, 1,5-diazabicyclo [4. , 3,0] -5-Nonene (Trademark: DBA), 1,8-diazabicyclo [5,4,0] -7-undecene (Trademark: DBU), DBU-phenol salt, DBU-octylic acid Examples thereof include salts and DBU-p-toluenesulfonate.
These (e) curing accelerators may be used alone or in combination of two or more.

When the said adhesive epoxy resin composition contains the said (e) hardening accelerator, the content is although it does not specifically limit, It is 0.1 to 10 weight% in the said adhesive epoxy resin composition. Preferably, it is 0.3-7 weight%, More preferably, it is 0.5-5 weight%.
When the content of the above (e) curing accelerator is less than 0.1% by weight, the curability may be lowered. Therefore, the curing conditions such as the curing time and the curing temperature must be strictly controlled, and workability may be reduced.

<(F) Organic solvent>
The organic solvent (f) is not particularly limited. For example, N-methylpyrrolidone; N, N-dimethylformamide; dimethyl sulfoxide; ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone; toluene, xylene, tetramethylbenzene Aromatic hydrocarbons such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Ethers; ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and the above-mentioned glycol ethers Esters such as chlorides; Alcohols such as ethanol, propanol, methanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha System solvents and the like.
These (f) organic solvents may be used alone or in combination of two or more.

When the said adhesive epoxy resin composition contains the said (f) organic solvent, the content is although it does not specifically limit, It is preferable that it is 20 to 300 weight% with respect to the said adhesive epoxy resin composition. .
If the content of the organic solvent (f) is less than 20% by weight, the viscosity may be increased, and if it exceeds 300% by weight, the curability may be lowered.

<(G) Adhesiveness imparting agent>
The (g) adhesiveness imparting agent is not particularly limited, and examples thereof include a coupling agent, a phenol resin, and an organic polyisocyanate.
Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, zircoaluminate-based, and titanium-based compounds, and partial hydrolysis condensates thereof. Among these coupling agents, silane coupling agents and partial hydrolysis-condensation products thereof are preferable because of their high adhesiveness-imparting effects.
The partially hydrolyzed condensate of the coupling agent may be a partially hydrolyzed condensate of the same or more coupling agents, or may be a partially hydrolyzed condensate of two or more coupling agents. .
Examples of the silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. The compound etc. which contain the alkoxy silyl group of these are mentioned.
These (g) adhesiveness imparting agents may be used alone or in combination of two or more.

When the said adhesive epoxy resin composition contains the said (g) adhesive imparting agent, the content is although it does not specifically limit, It is preferable that it is 3-30 weight% in the said adhesive epoxy resin composition. .
When the content of the above-mentioned (g) adhesiveness-imparting agent is less than 3% by weight, the adhesiveness may be lowered, and when it exceeds 30% by weight, the cost is increased, and workability and storage stability are deteriorated. Sometimes.

<Method for producing adhesive epoxy resin composition>
The adhesive epoxy resin composition comprises (a) an epoxy resin, (b) a reactive diluent, and (c) a curing agent, and further, if necessary, (d) a filler, (e) a curing accelerator. (F) Organic solvent, (g) It can obtain by mixing arbitrary components, such as adhesive provision agent.
A method of mixing these is not particularly limited, and a conventionally known method can be used. For example, a method of stirring using a stirrer, a method of kneading using a three-roll mill, or the like can be used.

<Hardened product>
A cured product can be obtained by curing the adhesive epoxy resin composition.
The method of curing the adhesive epoxy resin composition is not particularly limited, and examples thereof include a method of heating at 100 ° C. for 1 hour and then at 180 ° C. for 4 hours using a heating device.
It does not specifically limit as said heating apparatus, For example, a ventilation constant temperature dryer, a constant temperature constant temperature dryer, etc. can be used.

<Application>
The application of the adhesive epoxy resin composition is not particularly limited, and it is preferably used for any application as long as the metal is an adherend and adhesion is required with the metal. Can do.
Specifically, for example, a metal composition, a resin composition for forming an interlayer insulating film of a wiring board, a resin composition for impregnation for preparing a prepreg, and a resin composition for a sealant , Resin composition for heat dissipation material, resin composition for optical material, resin composition for metal foil-clad laminate, resin composition for fiber reinforced composite material, resin composition for electromagnetic wave shielding plate, resin composition for solar cell module, etc. And it can be used conveniently as a resin composition used for the site | part which requires the adhesiveness with a metal.

In particular, the adhesive epoxy resin composition can be suitably used as a resin composition for forming an interlayer insulating film of a wiring board.
The reason is that, as described above, the adhesive epoxy resin composition includes a reactive diluent mainly composed of an epoxy compound having (b) a specific structure (trifunctional structure having a trimethylolalkane skeleton). This is because, when it is made into a cured product, it has a property of being excellent in tensile shear adhesive strength and peel adhesive strength with a metal while having low viscosity.
Further, the adhesive epoxy resin composition is excellent in adhesion with Cu, which is a general material constituting a circuit of a wiring board, and this is also suitably used as a resin composition for forming an interlayer insulating film. This is one reason why it can.

As described above, the adhesive epoxy resin composition exhibits excellent adhesion with various metals after curing, and in particular, Cu, Al, Ga, In, Fe, Ni, Ag, Au, Pb, Mn Excellent adhesion between Ti, Cr, Mo, W, and Sn.

Moreover, when the said adhesive epoxy resin composition contains (d) filler, the said adhesive epoxy resin composition should be used suitably also as a resin composition for forming the heat radiating member provided in an electronic circuit board. Can do.
The reason is that, as described above, the adhesive epoxy resin composition includes a reactive diluent mainly composed of an epoxy compound having (b) a specific structure (trifunctional structure having a trimethylolalkane skeleton). (D) Even when a filler is blended, when it is a cured product, the adhesiveness does not decrease, and the tensile shear bond strength and peel adhesion with a metal member constituting an electronic circuit board such as a metal circuit It is because it has the characteristic that it is excellent in strength.

<< Interlayer insulating film forming film >>
Next, the interlayer insulating film forming film of the present invention will be described.
The film for forming an interlayer insulating film of the present invention is characterized by comprising the adhesive epoxy resin composition of the present invention.
The film for forming an interlayer insulation film is usually a film made of the adhesive epoxy resin composition of the present invention formed on a support film having excellent releasability.

The support film is not particularly limited, and examples thereof include films made of polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, and polycarbonates. The support film may be subjected to surface treatment such as treatment of the surface with a release agent.

As a method of forming the adhesive epoxy resin composition on the support film, the adhesive epoxy resin composition is conventionally known, for example, curtain coating, roll coating, spray coating, bar coating, screen printing, etc. After applying by this method, there may be mentioned a method of drying and removing an organic solvent or the like, if necessary.

The interlayer insulating film-forming film may be a semi-cured state (B-stage state) of the adhesive epoxy resin composition applied on the support film, and further completely cured. It may be.

The interlayer insulating film-forming film may have a metal circuit pattern or a solid conductor layer formed on one side and / or both sides thereof.
What is necessary is just to form the said metal circuit pattern and conductor layer by conventionally well-known methods, such as plating and vapor deposition, for example.

Such a film for forming an interlayer insulating film can be suitably used as a material for forming an interlayer insulating film of a multilayer wiring board.

<< wiring board >>
Next, the wiring board of the present invention will be described.
The wiring board of the present invention includes an interlayer insulating film made of the adhesive epoxy resin composition of the present invention.
That is, the insulating layer which comprises a wiring board is formed with the said adhesive epoxy resin composition.
Hereinafter, the wiring board of the present invention will be described by taking as an example a case where the wiring board is a build-up wiring board in which a build-up layer is laminated on an inner layer circuit board.
Of course, the wiring board of the present invention is not limited to the above-mentioned buildup wiring board, and may be a buildup wiring board in which all layers are composed only of the buildup layer, or the adhesive epoxy resin of the present invention. A single-layer board in which a metal circuit is formed on one surface of a single interlayer insulating film made of the composition may be used, or another multilayer wiring board may be used.

In the build-up wiring board, interlayer insulating films and conductive layers (metal circuits) made of the adhesive epoxy resin composition of the present invention are alternately laminated on an inner layer circuit board.
As a method for producing such a build-up wiring board, specifically, for example,
(1) After laminating the interlayer insulating film forming film on the inner layer circuit board, the interlayer insulating film forming film is cured, and via holes are formed as necessary to form an interlayer insulating film. Thereafter, a conductor circuit made of metal is formed on the interlayer insulating film by a conventionally known method such as a subtractive method or an additive method. A method of producing a build-up wiring board by repeating the step of forming the interlayer insulating film and the step of forming the conductor circuit can be employed.
At this time, as the interlayer insulating film forming film, an interlayer insulating film forming film having a circuit pattern or a solid conductor layer laminated on the surface thereof may be used.

For example,
(2) After applying the adhesive epoxy resin composition on the inner circuit board, the applied adhesive epoxy resin composition is cured, and via holes are formed as necessary to form an interlayer insulating film. Thereafter, a conductor circuit made of metal is formed on the interlayer insulating film by a conventionally known method such as a subtractive method or an additive method. A method of producing a build-up wiring board by repeating the step of forming the interlayer insulating film and the step of forming the conductor circuit can be employed.
Here, the method for applying the adhesive epoxy resin composition is not particularly limited, and a known method can be used. Examples thereof include curtain coating, roll coating, spray coating, and screen printing. .

Moreover, you may perform hardening of the said adhesive epoxy resin composition, pressing as needed. By applying pressure, the tensile shear adhesiveness and peel adhesiveness between the interlayer insulating film and the conductor circuit can be further enhanced.
When the curing of the adhesive epoxy resin composition is performed while applying pressure, the method of applying pressure is not particularly limited, and examples thereof include a method of applying pressure using a pressure roll. The pressure is not particularly limited, but is preferably 0.1 to 20 MPa, and more preferably 0.2 to 15 MPa. If the pressure is less than 0.1 MPa, the effect of improving the tensile shear adhesion and peel adhesion between the interlayer insulating film and the conductor circuit may not be obtained. If the pressure exceeds 20 MPa, the thickness of the interlayer insulating film may be reduced. It may not be possible to adjust.

In the wiring board of the present invention, examples of the metal constituting the conductor circuit include Cu, Ni, Cr, Sn, Ag, and Al.

In the wiring board of the present invention, the thickness of the interlayer insulating film is not particularly limited, but is preferably 0.5 to 300 μm, and more preferably 20 to 40 μm.
If the thickness of the interlayer insulating film is less than 0.5 μm, insulation between the layers may not be secured. If the thickness exceeds 300 μm, it is not suitable for a thin wiring board and it takes time to form a via hole. Also, the cost may be high.

Since the wiring board of the present invention includes an interlayer insulating film made of the adhesive epoxy resin composition of the present invention, the metal circuit and the interlayer insulating film have high adhesion, and the occurrence of peeling of the metal circuit is prevented. It can be avoided and has excellent reliability.

<< Electronic circuit board >>
Next, the electronic circuit board of the present invention will be described.
The electronic circuit board of the present invention is characterized by including a heat dissipating member made of an adhesive epoxy resin composition containing the filler (d) of the present invention.
The electronic circuit board is obtained by mounting a semiconductor element such as an IC chip on a wiring board such as a build-up board as described above and further forming a heat dissipation member.

Here, the said heat radiating member is formed using the adhesive epoxy resin composition containing (d) filler among the adhesive epoxy resin compositions of this invention. At this time, it is preferable that (d) the filler contains boron nitride. This is because the thermal conductivity is high and the thermal expansion coefficient is low.
The method for forming the heat radiating member is not particularly limited. For example, the adhesive epoxy resin composition is previously processed into an uncured, semi-cured or cured sheet, and this is a wiring on which a semiconductor element is mounted. It may be formed by affixing to a board and then curing as necessary, or after directly supplying the adhesive epoxy resin composition by coating or the like to a wiring board on which a semiconductor element is mounted, a curing treatment is performed. You may form by doing.

In the electronic circuit board, the heat dissipation member is preferably formed so as to be in contact with a metal member such as a metal circuit. This is because the heat dissipating member is excellent in adhesion to metal.
Moreover, when forming the said heat radiating member, in each surface (front surface and back surface) of an electronic circuit board, you may form so that the whole may be covered, and you may form so that it may exist only in part.

Since such an electronic circuit board includes a heat radiating member made of an adhesive epoxy resin composition containing the filler (d) of the present invention, the metal member such as a metal circuit and the heat radiating member have high adhesion. It becomes. Therefore, an air layer or the like that can be a barrier during heat conduction is unlikely to intervene, and heat can be radiated efficiently.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples of the present invention, but the present invention is not limited to the following examples. In the following, “%” means “% by weight” unless otherwise specified.

[Synthesis example]
(B) As the reactive diluent, reactive diluent (b1) (reactive diluent A) mainly composed of trimethylolpropane triglycidyl ether was synthesized by the following method.
In a 1 L SUS four-necked flask equipped with a reflux condenser, a nitrogen blowing tube, and a thermometer, 127.2 g (0.5 mol) of trimethylolpropane triallyl ether, 200 g (6.25 mol) of methanol, and 123.1 g of acetonitrile ( 3 mol) and 45.8 g (0.38 mol) of sodium silicate (manufactured by Kishida Chemical Co., Ltd.) with an internal temperature of 40 ° C.
While stirring, 291.4 g (3 mol) of 35% aqueous hydrogen peroxide was slowly added dropwise over 5 hours while stirring, and then stirred for 8 hours to react. The peroxide concentration in the system at the end of the reaction was 0.21%. Thereafter, extraction with toluene was performed, and the peroxide was removed by washing with water, followed by concentration to obtain a reactive diluent (b1) at a yield of 80%. The reactive diluent (b1) obtained had a gas chromatography (GC) purity of 95.4%, an epoxy equivalent of 118 g / eq, a viscosity of 123 mPa · s, and a total chlorine content of 92 ppm.

In addition to the reactive diluent A obtained in the above synthesis example, the following epoxy resin, reactive diluent, curing agent, curing accelerator and filler were used. The abbreviations of the raw materials are also shown.
(Epoxy resin)
Epoxy resin A: phenol novolac type epoxy resin (manufactured by DIC, EPICLON N-730A, liquid, epoxy equivalent 175 g / eq, viscosity 4500 Pa · s)
Epoxy resin B: Triphenylmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER 1032H60, solid, epoxy equivalent 170 g / eq)

(Reactive diluent)
Reactive diluent B: Reactive diluent based on trimethylolpropane triglycidyl ether (manufactured by Nagase Chemtex, EX-321, liquid, GC purity 75%, epoxy equivalent 141 g / eq, viscosity 132 mPa · s , Total chlorine amount 74000ppm)
Reactive diluent C: Reactive diluent based on p-tert-butylphenylglycidyl ether (manufactured by Nagase ChemteX Corporation, EX-146, liquid, epoxy equivalent 225 g / eq, viscosity 20 mPa · s, total chlorine (Amount 3000ppm)
Reactive diluent D: Reactive diluent based on ethylene glycol diglycidyl ether (manufactured by Nagase ChemteX Corporation, EX-810, liquid, epoxy equivalent 113 g / eq, viscosity 20 mPa · s, total chlorine amount 6000 ppm)

(Curing agent)
Curing agent A: 2-ethyl-4-methylimidazole (Mitsubishi Chemical Corporation, EMI24, amine equivalent 110 g / eq)
Curing agent B: phenol novolac resin (manufactured by Sumitomo Bakelite, PR-HF-6)
(Curing accelerator)
Curing accelerator A: Triphenylphosphine (Hokuko TPP, manufactured by Hokuko Chemical Co., Ltd.)
(filler)
Filler A: silicon dioxide (manufactured by Tatsumori, MSR-2212)
Filler B: Boron nitride (manufactured by Showa Denko KK, UHP-1K)

Measurements and evaluations in the above synthesis examples and the following examples and comparative examples were performed by the following methods.
[Gas chromatography (GC) purity]
It measured using the gas chromatograph (Shimadzu Corp. make, GC-2010).
In addition, MPS-50 (made by Quadrex) was used as the column, and He gas was used as the carrier gas.
[End of reaction]
The time when the reaction rate (epoxidation rate) reached 95% or more by a gas chromatograph (manufactured by Shimadzu Corporation, GC-2010) was defined as the end point of the reaction.
[Epoxy equivalent]
The epoxy equivalent was measured according to JIS K 7236.
[Total chlorine content]
The total chlorine content of the product was measured according to JIS K 7243-3.
In the examples and comparative examples, the total chlorine amount was measured as the total halogen amount of the reactive diluents A to D. Reactive diluents B to D are synthesized using polyhydric alcohol and epichlorohydrin as raw materials, and reactive diluents A to D use raw materials containing halogen other than chlorine as raw materials at the time of synthesis. Not done. Therefore, in the reactive diluents A to D, it can be considered that the total chlorine amount is substantially the same as the total halogen amount.
[Reaction rate]
GC measurement was performed using a gas chromatograph (manufactured by Shimadzu Corporation, GC-2010), and the reaction rate was calculated from the area ratio of the raw material (olefin compound) and product (epoxy compound).
[viscosity]
About the adhesive epoxy resin composition, the viscosity in 25 degreeC was measured using the viscometer (the Toki Sangyo company make, B-type viscometer).
[Tensile shear bond strength]
Degrease Cu plate (Engineering Test Service, length 150mm x Width 25mm x Thickness 1.5mm) and Al plate (Engineering Test Service, length 150mm x Width 25mm x Thickness 1.5mm) with acetone Thereafter, the adhesive epoxy resin composition was thinly applied, and the Cu plate and the Al plate were overlapped at an overlap distance of 12.5 mm. Then, it fixed with the scissors tool and produced the test piece by hardening at 100 degreeC for 1 hour and 180 degreeC for 4 hours. The test was performed using a strograph (manufactured by Toyo Seiki Seisakusho, VG20-E), the test was started at a tensile speed of 5 mm / min, and the load when the test piece broke was regarded as the tensile shear bond strength. Tensile shear bond strength was evaluated in three stages according to the following criteria.
A: 20 N / mm ² or more B: 10 N / mm ² or more, less than 20 N / mm ² ×: less than 10 N / mm ² [90 ° peel adhesion strength]
An adhesive epoxy resin composition is sandwiched between a 35 μm thick copper foil and an aluminum plate having a thickness of 1 mm, cured by pressure bonding at 175 ° C. for 10 minutes, and then cured at 175 ° C. for 3 hours. A test piece was prepared (resin film thickness 0.15 mm). Thereafter, the 90 ° peel adhesive strength of a 10 mm wide copper foil was measured at a rate of 50 mm / min using a strograph (manufactured by Toyo Seiki Seisakusho, VG20-E).
The measured peel adhesive strength was evaluated in three stages according to the following criteria.
A: 2 N / cm or more ○: 1 N / cm or more, less than 2 N / cm x: less than 1 N / cm

[Example 1]
10% of epoxy resin A, 5% of reactive diluent A, 5% of curing agent A and 80% of filler A were mixed to obtain an adhesive epoxy resin composition.
Using the obtained adhesive epoxy resin composition, the viscosity, the total chlorine content of the epoxy resin and reactive diluent constituting the viscosity were measured, and the tensile shear bond strength was evaluated. The results are shown in Table 1.

[Comparative Examples 1 and 2]
The same procedure as in Example 1 was performed except that the composition of the adhesive epoxy resin composition was changed as shown in Table 1. The results are shown in Table 1.

The adhesive epoxy resin composition obtained in Example 1 of Table 1 has, as a reactive diluent, (b) an epoxy compound having a specific structure (trifunctional structure having a trimethylolalkane skeleton) as a main component. Since it contains a reactive diluent, the tensile shear bond strength was excellent. On the other hand, the adhesive epoxy resin compositions obtained in Comparative Examples 1 and 2 are (b) an epoxy compound having a specific structure instead of a reactive diluent mainly composed of an epoxy compound having a specific structure. Since it contains a reactive diluent (a linear reactive diluent whose epoxy group is monofunctional or bifunctional) that is not a main component, the reactivity is lowered and the tensile shear bond strength is poor.

[Example 2]
40% of epoxy resin B, 15% of reactive diluent A, 40% of curing agent B, and 5% of curing accelerator A were mixed to obtain an adhesive epoxy resin composition.
Using the obtained adhesive epoxy resin composition, 90 ° peel adhesive strength was evaluated. The results are shown in Table 2.

[Examples 3 to 6]
The same procedure as in Example 2 was performed except that the composition of the adhesive epoxy resin composition was changed as shown in Table 2. The results are shown in Table 2.

[Comparative Examples 3 and 4]
The same procedure as in Example 2 was performed except that the composition of the adhesive epoxy resin composition was changed as shown in Table 2. The results are shown in Table 2.

The adhesive epoxy resin compositions obtained in Examples 2 to 6 in Table 2 are mainly composed of an epoxy compound having a specific structure (trifunctional structure having a trimethylolalkane skeleton) as a reactive diluent. Because it contains a reactive diluent, it has excellent 90 ° peel adhesive strength. On the other hand, the adhesive epoxy resin composition obtained in Comparative Examples 3 and 4 includes (b) a reactive diluent whose main component is an epoxy compound having a specific structure (trifunctional structure having a trimethylolalkane skeleton). Since it does not contain, it was inferior to 90 degree peel adhesive strength.
Further, when Example 5 is compared with Example 6, (b) a reactive diluent mainly composed of trimethylolpropane triglycidyl ether as a reactive diluent mainly composed of an epoxy compound having a specific structure. When (b1) is used, the epoxy equivalent is 101 to 120 g / eq, the viscosity is 50 to 130 mPa · s, and the total chlorine content is 100 ppm or less and contains a high-purity reactive diluent (b1). The adhesive epoxy resin composition of Example 5 was particularly excellent in 90 ° peel adhesive strength, whereas a low-purity reactive diluent (b1) that did not satisfy the above-mentioned epoxy equivalent, viscosity, and total chlorine content was used. The adhesive epoxy resin composition of Example 6 contained was somewhat inferior in 90 ° peel adhesive strength.

Claims (11)

(A) epoxy resin (however, excluding an epoxy compound represented by the following general formula (1) and trimethylolmethane triglycidyl ether), (b) an epoxy compound or trimethylolmethane represented by the following general formula (1) An adhesive epoxy resin composition comprising a reactive diluent containing 50 wt% or more of triglycidyl ether, (c) a curing agent, and (d) boron nitride.

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.) The adhesive epoxy resin composition according to claim 1, wherein the content of (b) the reactive diluent is 5 to 95% by weight based on the total amount of (a) the epoxy resin and (b) the reactive diluent. object. The adhesive epoxy resin composition according to claim 1 or 2, wherein (b) the reactive diluent is a reactive diluent (b1) containing trimethylolpropane triglycidyl ether. The reactive diluent (b1) has an epoxy equivalent of 101 to 120 g / eq, a total halogen content of 100 ppm or less, and a viscosity at 25 ° C of 50 to 130 mPa · s. Adhesive epoxy resin composition. (A) Epoxy resin is biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene phenol addition Reactive epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol phenol co-condensed novolac type epoxy resin, naphthol cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin Type epoxy resin, biphenyl novolac type epoxy resin, ethylphenol novolac type epoxy resin, butylphenol novolac type Xy resin, octylphenol novolac epoxy resin, phenol novolac epoxy resin containing xylylene skeleton, phenol novolac epoxy resin containing fluorene skeleton, 4,4'-biphenylphenol epoxy resin, tetramethyl-4,4'-biphenol epoxy resin Dimethyl-4,4′-biphenylphenol type epoxy resin, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis (4-hydroxyphenyl) ethyl) phenyl] propane type epoxy resin, 2 , 2′-methylenebis (4-methyl-6-tert-butylphenol) type epoxy resin, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) type epoxy resin, trishydroxyphenylmethane type epoxy resin, resorci Type epoxy resin, hydroquinone type epoxy resin, pyrogallol type epoxy resin, diisopropylidene type epoxy resin, 1,1-di-4-hydroxyphenylfluorene type epoxy resin, phenolized polybutadiene type epoxy resin, 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-cyclohexylcarboxylate type epoxy resin, 1,4-butanediol type epoxy resin, 1,6-hexanediol type epoxy resin, polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, pentaerythritol Type epoxy resin, xylylene glycol derivative type epoxy resin, isocyanuric ring type epoxy resin, hydantoin ring type epoxy resin, hexahydrophthalic acid diglycidyl ester type epoxy resin, tetra Hydrophthalic acid diglycidyl ester type epoxy resin, aniline type epoxy resin, toluidine type epoxy resin, p-phenylenediamine type epoxy resin, m-phenylenediamine type epoxy resin, diaminodiphenylmethane derivative type epoxy resin, diaminomethylbenzene derivative type epoxy resin, The adhesive epoxy resin composition according to any one of claims 1 to 4, which is at least one selected from a brominated phenol novolac-type epoxy resin and a brominated cresol novolac-type epoxy resin. (C) The curing agent is 2-ethyl-4-methylimidazole, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, boron trifluoride-amine complex, guanidine derivative, dicyandiamide, linolene. Polyamide resin synthesized by dimer of acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydro anhydride Addition of phthalic acid, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol Resins, phenol aralkyl resins, polyhydric phenol novolak resins synthesized from polyvalent hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylol methane resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol phenol co-condensed novolak resins, naphthols The cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, and at least one selected from the group consisting of alkoxy group-containing aromatic ring-modified novolak resins. The adhesive epoxy resin composition according to any one of the above. The adhesive epoxy resin composition of any one of Claims 1-6 used for formation of the heat radiating member provided in an electronic circuit board. An electronic circuit board comprising a heat radiating member made of the adhesive epoxy resin composition according to claim 1. (A) epoxy resin (however, excluding an epoxy compound represented by the following general formula (1) and trimethylolmethane triglycidyl ether), (b) an epoxy compound or trimethylolmethane represented by the following general formula (1) The adhesive epoxy resin composition used for formation of the interlayer insulation film containing the reactive diluent containing 50 wt% or more of triglycidyl ether, and (c) hardening | curing agent.

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.) (A) epoxy resin (however, excluding an epoxy compound represented by the following general formula (1) and trimethylolmethane triglycidyl ether), (b) an epoxy compound or trimethylolmethane represented by the following general formula (1) A film for forming an interlayer insulating film comprising a reactive diluent containing 50 wt% or more of triglycidyl ether and an adhesive epoxy resin composition containing (c) a curing agent.

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.) (A) epoxy resin (however, excluding an epoxy compound represented by the following general formula (1) and trimethylolmethane triglycidyl ether), (b) an epoxy compound or trimethylolmethane represented by the following general formula (1) A wiring board comprising an interlayer insulating film made of an adhesive epoxy resin composition containing a reactive diluent containing 50 wt% or more of triglycidyl ether and (c) a curing agent.

(However, R ^{1 to} R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may be the same or different. R ⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.)