JP2014040536A - Curable resin composition and conductive adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in coating properties, conductivity, adhesiveness, and heat radiation, which produces a cured material excellent in heat resistance and durability with less secular change of these properties in a high temperature state; and a conductive adhesive including the curable resin composition.SOLUTION: A curable resin composition includes: a polyimide silicone resin (A) represented by the following formula (1) having a phenolic hydroxyl group; an epoxy resin (B); a conductive metal powder (C); silica (D), and an organic solvent (E). In the formula, X represents a tetracarboxylic acid residue, Y and Z represent a bisphenol group and a diamine residue having a siloxane structure, respectively, and W represents a diamine residue other than Y and Z. The curable resin composition may be used as a conductive adhesive, improving the productivity of an LED.

Description

  The present invention relates to a polyimide silicone resin / epoxy resin-based curable resin composition containing a conductive metal powder, and a conductive adhesive containing the curable resin composition.

  Conventionally, when manufacturing a light emitting diode (LED) component by a lamp type or SMD (surface mount component) type, a conductive epoxy resin adhesive is used to bond the LED chip and the lead frame. Has been. In particular, when the joined body of the LED chip and the lead frame is exposed to a high temperature state in the wire bonding process, a polyfunctional epoxy resin that gives a heat-resistant cured product is used as a binder for the adhesive.

  In recent years, LEDs are used in a wide range of applications such as electronic equipment pilot lamps, automobiles, LCD TV backlights, traffic lights, electric bulletin boards, etc. due to their long product life and fast response speed. Applications are expected to expand. In addition, it is also used for lighting because of its extremely high energy efficiency compared to conventional lighting fixtures such as light bulbs and fluorescent lamps.

  For lighting applications, it is necessary to use high-brightness LED components, and it is necessary to pass a current several times that of conventional general-purpose LEDs. As a result, a certain amount of heat is generated from the LED chip, and the LED component is exposed to a high temperature state for a long time. When LED parts are manufactured using a conventional epoxy resin-based conductive adhesive, the adhesive layer is not sufficiently heat resistant over time, so the adhesive layer gradually deteriorates and the performance of the LED parts decreases. Or the color changed.

  Therefore, Patent Document 1 (Japanese Patent Application Laid-Open No. 2005-113059) provides an LED component with little deterioration over time by using a conductive adhesive using polyimide silicone having a specific structure with high heat resistance and high strength. It has been proposed.

  However, since the polyimide silicone varnish has very good wettability, when the paste obtained by diluting the composition of Patent Document 1 with a solvent is applied to a substrate of an LED component or the like, the paste spreads too much and more than the portion to be applied. There was a drawback that the paste diffused. In order to prevent the paste from spreading too much, it is conceivable to increase the viscosity by reducing the amount of solvent to be used. In this case, however, there is a problem that stringing at the time of application becomes remarkable.

JP 2005-113059 A

  Therefore, the present invention can apply the paste only to the necessary part, has no stringing at the time of application, is excellent in so-called applicability, is excellent in conductivity, adhesiveness, heat dissipation, and high temperature state of these characteristics It aims at providing the curable resin composition which gives the hardened | cured material excellent in heat resistance and durability with little time-dependent change in, and the conductive adhesive containing this curable resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have combined an epoxy resin, a polyimide silicone resin having a curing reactive group, a conductive metal powder, silica, and an organic solvent. The inventors have obtained the knowledge that a cured product having excellent coating properties and heat resistance and durability of various physical properties can be obtained, and the present invention has been completed based on the knowledge.

［式中、Ｘはテトラカルボン酸成分に由来するテトラカルボン酸残基であり、Ｙは下記一般式（２）：

（式中、Ａは単結合、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、又は−ＳＯ₂−である。）
で表される２価の基であり、（Ａ）成分の分子中にＡが複数存在する場合には、それらのＡは同一又は異なり、Ｚは下記一般式（３）：

（式中、Ｒは独立に炭素原子数１〜８の１価炭化水素基であり、ａは１〜１２０の整数である。）
で表される２価の基であり、Ｗは２個以上のフェノール性水酸基を有するジアミン化合物及びシロキサン構造を有するジアミン化合物以外のジアミン化合物に由来するジアミン残基である。ｐは１０〜８０モル％、ｑは５〜５０モル％、ｒは０〜５０モル％で、ｐ＋ｑ＋ｒは１００モル％となる数である。］
によって表される、繰り返し単位（ａ）、繰り返し単位（ｂ）、及び場合により繰り返し単位（ｃ）によって構成され、１分子中に２個以上のフェノール性水酸基を有するポリイミドシリコーン樹脂、
（Ｂ）エポキシ樹脂、
（Ｃ）導電性金属粉末、
（Ｄ）シリカ、及び
（Ｅ）有機溶剤
を含有することを特徴とする硬化性樹脂組成物。
〔２〕 前記（Ａ）成分において、前記繰り返し単位（ａ）の含有割合ｐが１０〜８０モル％であり、前記繰り返し単位（ｂ）の含有割合ｑが５〜５０モル％であり、前記繰り返し単位（ｃ）の含有割合ｒが１〜５０モル％であり、ただし、前記繰り返し単位（ａ）〜（ｃ）の含有割合の合計が１００モル％である〔１〕記載の硬化性樹脂組成物。
〔３〕 Ｗが下記一般式（４）：

（式中、Ｂは

から選ばれる基であり、（Ａ）成分の分子中にＢが複数存在する場合には、それらのＢは同一又は異なる。）
で表される２価の基である〔１〕又は〔２〕記載の硬化性樹脂組成物。
〔４〕 前記（Ｃ）成分が、銀粉末である〔１〕〜〔３〕のいずれかに記載の硬化性樹脂組成物。
〔５〕 前記（Ａ）成分１００質量部と、前記（Ｂ）成分０．１〜３０質量部と、前記（Ｃ）成分４００〜３，０００質量部と、前記（Ｄ）成分１〜１００質量部と、前記（Ｅ）成分５０〜１，０００質量部とを含む〔１〕〜〔４〕のいずれかに記載の硬化性樹脂組成物。
〔６〕 高輝度発光ダイオード部品の製造用である〔１〕〜〔５〕のいずれかに記載の硬化性樹脂組成物。
〔７〕 ＬＥＤチップとリードフレーム又はＬＥＤパッケージで使用されるツェナーダイオードとリードフレームとの接着用である〔６〕記載の硬化性樹脂組成物。
〔８〕 〔１〕〜〔７〕のいずれかに記載の硬化性樹脂組成物を含む導電性接着剤。 That is, this invention provides the following curable resin composition and the conductive adhesive containing this curable resin composition.
[1] (A) The following formula (1):

[Wherein, X is a tetracarboxylic acid residue derived from a tetracarboxylic acid component, and Y is the following general formula (2):

(In the formula, A is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or —SO ₂ —).
When a plurality of A are present in the molecule of the component (A), these A are the same or different, and Z is the following general formula (3):

(In the formula, R is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 1 to 120.)
W is a diamine residue derived from a diamine compound other than a diamine compound having two or more phenolic hydroxyl groups and a diamine compound having a siloxane structure. p is 10 to 80 mol%, q is 5 to 50 mol%, r is 0 to 50 mol%, and p + q + r is a number that is 100 mol%. ]
Represented by: a polyimide silicone resin composed of a repeating unit (a), a repeating unit (b), and optionally a repeating unit (c) and having two or more phenolic hydroxyl groups in one molecule;
(B) epoxy resin,
(C) conductive metal powder,
A curable resin composition comprising (D) silica and (E) an organic solvent.
[2] In the component (A), the content p of the repeating unit (a) is 10 to 80 mol%, the content q of the repeating unit (b) is 5 to 50 mol%, and the repetition [1] The curable resin composition according to [1], wherein the content ratio r of the unit (c) is 1 to 50 mol%, provided that the total content ratio of the repeating units (a) to (c) is 100 mol%. .
[3] W is the following general formula (4):

(Where B is

When a plurality of B are present in the molecule of the component (A), these B are the same or different. )
The curable resin composition according to [1] or [2], which is a divalent group represented by:
[4] The curable resin composition according to any one of [1] to [3], wherein the component (C) is silver powder.
[5] 100 parts by mass of the component (A), 0.1-30 parts by mass of the component (B), 400-3,000 parts by mass of the component (C), and 1-100 parts by mass of the component (D). Part and the curable resin composition in any one of [1]-[4] containing the said (E) component 50-1,000 mass parts.
[6] The curable resin composition according to any one of [1] to [5], which is for producing a high-luminance light-emitting diode component.
[7] The curable resin composition according to [6], which is used for bonding a Zener diode and a lead frame used in an LED chip and a lead frame or an LED package.
[8] A conductive adhesive comprising the curable resin composition according to any one of [1] to [7].

  The composition according to the present invention is useful as a conductive adhesive, improves the productivity of the LED, and satisfies the characteristics of high heat resistance and high thermal conductivity that are indispensable for a high-brightness LED. The heat generated from the LED chip is effectively transmitted to the lead frame to be dissipated, and the initial performance can be maintained even when exposed to a high temperature for a long time.

Hereinafter, the present invention will be described in detail.
First, the curable resin composition of the present invention will be described.

［式中、Ｘはテトラカルボン酸成分に由来するテトラカルボン酸残基であり、Ｙは下記一般式（２）：

（式中、Ａは単結合、−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、又は−ＳＯ₂−である。）
で表される２価の基であり、（Ａ）成分の分子中にＡが複数存在する場合には、それらのＡは同一又は異なり、Ｚは下記一般式（３）：

（式中、Ｒは独立に炭素原子数１〜８の１価炭化水素基であり、ａは１〜１２０の整数である。）
で表される２価の基であり、Ｗは２個以上のフェノール性水酸基を有するジアミン化合物及びシロキサン構造を有するジアミン化合物以外のジアミン化合物に由来するジアミン残基である。ｐは１０〜８０モル％、ｑは５〜５０モル％、ｒは０〜５０モル％で、ｐ＋ｑ＋ｒは１００モル％となる数である。］ [(A) Polyimide silicone resin]
The polyimide silicone resin (A) according to the present invention has a repeating unit (a), a repeating unit (b), and an arbitrary unit represented by the following formula (1) having two or more phenolic hydroxyl groups in one molecule. Of repeating units (c).
(A) The following formula (1):

[Wherein, X is a tetracarboxylic acid residue derived from a tetracarboxylic acid component, and Y is the following general formula (2):

(In the formula, A is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or —SO ₂ —).
When a plurality of A are present in the molecule of the component (A), these A are the same or different, and Z is the following general formula (3):

(In the formula, R is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 1 to 120.)
W is a diamine residue derived from a diamine compound other than a diamine compound having two or more phenolic hydroxyl groups and a diamine compound having a siloxane structure. p is 10 to 80 mol%, q is 5 to 50 mol%, r is 0 to 50 mol%, and p + q + r is a number that is 100 mol%. ]

  In addition, p, q, and r are repeating units (a), (b), and (c), respectively, p = 10-80 mol%, q = 5-50 mol%, r = 0-50 mol% (used). In this case, the number is 1 to 50 mol%, but preferably p is 20 to 60 mol%, q is 10 to 45 mol%, and r is 5 to 40 mol%.

  The weight average molecular weight of the polyimide silicone resin of the component (A) has good compatibility with other composition components such as a solvent, and the adhesion, strength and elasticity of the cured product of the composition of the present invention with the substrate are improved. In order to be sufficient, the weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent is usually 5,000 to 150,000, preferably 10,000 to 70,000. Is good.

  As described above, the polyimide silicone resin of the component (A) of the composition of the present invention has two or more phenolic hydroxyl groups in one molecule. And this (A) component forms a hardened | cured material integrally with the epoxy resin of the (B) component mentioned later, and can provide heat resistance and durability to the said hardened | cured material. In addition, it is preferable that this (A) component is soluble in an organic solvent, and is colorless and transparent.

  The said (A) component of this invention can be obtained by the method similar to the synthesis | combination of a well-known polyimide. That is, it is obtained by reacting (x) a tetracarboxylic acid or its monoanhydride, dianhydride, monoester, diester or other derivative (hereinafter referred to as “tetracarboxylic acid component”) with (y) a diamine compound. be able to.

(X) Tetracarboxylic acid component The tetracarboxylic acid component used for preparing the polyimide silicone resin of the component (A) of the present invention is not particularly limited, and all those conventionally used for polyimide synthesis are used. can do.

Preferred examples thereof include those having the structure shown below.

  The tetracarboxylic acid component of component (x) can be used alone or in combination of two or more.

(Y) Diamine Compound For the preparation of the component (A) of the present invention, as the (y) diamine compound to be reacted with the tetracarboxylic acid component of the component (x), for example, at least two diamine compounds are combined. Must be used. That is, it is necessary to use (y1): a diamine compound having two or more phenolic hydroxyl groups and (y2): a diamine compound having a siloxane structure. In addition, (y3): diamine compounds other than (y1) and (y2) may be used in combination.

  Alternatively, in place of the two types of diamine compounds of the components (y1) and (y2), a diamine compound having a siloxane structure together with at least two phenolic hydroxyl groups may be used. A polyimide silicone resin can be prepared.

<(Y1) Diamine Compound Having Phenolic Hydroxyl Group>
The (y1) component diamine compound is a diamine compound having a phenolic hydroxyl group and having two or more hydroxyl groups. The two or more hydroxyl groups are substituted and bonded to the same or different aromatic rings.

  Here, in the present invention, the phenolic hydroxyl group means an aromatic hydrocarbon or a structure in which a hydrogen atom bonded to a carbon atom forming an aromatic ring skeleton of an aromatic hydrocarbon group is substituted with a hydroxyl group. It means a hydroxyl group.

（式中、Ａは単結合又は２価の有機基である。）
で表されるジアミン化合物が挙げられる。 The component (y1) is preferably the following general formula (5):

(In the formula, A is a single bond or a divalent organic group.)
The diamine compound represented by these is mentioned.

Examples of the divalent organic group in the above formula include —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —SO ₂ — and the like.

Preferable specific examples of the diamine compound represented by the general formula (5) include those having the structure shown below.

  This component (y1) can be used alone or in combination of two or more.

<(Y2) Diamine Compound Having Siloxane Structure>
The diamine compound as the component (y2) has at least one siloxane bond (Si—O—Si) in its structure.

（式中、Ｒは独立に炭素原子数１〜８、特に１〜６の１価炭化水素基であり、ａは１〜１２０、好ましくは１〜６０の整数である。）
で表されるジアミン化合物が挙げられる。 The component (y2) is preferably the following general formula (6):

(In the formula, R is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, and a is an integer of 1 to 120, preferably 1 to 60.)
The diamine compound represented by these is mentioned.

R in the above formula (6) is, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, isobutyl, butyl, tert-butyl, pentyl, neopentyl, hexyl, etc .; cyclopentyl Groups, cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, isobutenyl groups, hexenyl groups; cycloalkenyl groups such as cyclohexenyl groups; aryls such as phenyl groups; Group and the like. Among these, a methyl group and a phenyl group are preferable from the viewpoint of easy availability of raw materials.
In addition, the a is preferably an integer in the above range in order not to reduce the adhesion of the cured product of the present invention to the substrate.

  Preferable specific examples of the diamine compound represented by the general formula (6) include those having the structure shown below.

  This component (y2) can be used alone or in combination of two or more.

（式中、Ｂは２価の有機基である。）
で表されるエーテル結合を有するジアミン化合物が挙げられる。 <(Y3): Diamine compound other than (y1) and (y2)>
As the component (y3), for example, the following general formula (7):

(In the formula, B is a divalent organic group.)
The diamine compound which has an ether bond represented by these is mentioned.

Examples of B in the above formula (7) include the following divalent organic groups.

  Preferable specific examples of the diamine compound represented by the general formula (7) include those having the structure shown below.

  This component (y3) can be used alone or in combination of two or more.

<Use ratio of diamine compound>
As described above, when the diamine compound (y1), (y2), and optionally (y3) is used for the preparation of the polyimide silicone resin as the component (A) of the composition of the present invention, the above (A) In order to impart curability to the component polyimide silicone resin and to ensure sufficient adhesion, strength and elasticity to the substrate of the cured product of the composition of the present invention, the above (y1), (y2) and (y3) )), The above (y1): diamine compound having a phenolic hydroxyl group is usually 10 to 80 mol%, preferably 20 to 60 mol%, and (y2): siloxane. The diamine compound having a structure is usually 5 to 50 mol%, preferably 10 to 45 mol%, and diamine compounds other than the above (y3) :( y1) and (y2) are usually 0 to 50 mol%. Le%, when used, 1 to 50 mol%, and it is preferably used in combination as an amount in the range of 5 to 40 mol%.

<Preparation of (A) polyimide silicone resin>
The polyimide silicone resin which is the component (A) of the composition of the present invention is prepared by substantially equimolar amounts of the (x) tetracarboxylic acid component and the (y) diamine compound (mixture) according to a known polyimide synthesis method. It can be prepared by using and reacting. Specifically, it can be prepared by a one-stage polymerization method under high temperature reaction conditions. In addition, the above components (x) and (y) are dissolved in a solvent such as cyclohexanone and N-methyl-2-pyrrolidone, and reacted at a relatively low temperature (about 10 to 50 ° C.) to form a polyamic which is a polyimide precursor. An acid can be obtained and then prepared by a two-stage polymerization method in which dehydration and cyclization is carried out under high temperature conditions to form an imide ring structure.

  Here, the ratio of the (y) diamine compound (mixture) to 1 mol of the (x) tetracarboxylic acid component can be appropriately determined according to the setting of the desired molecular weight of the polyimide silicone resin. The range is 95 to 1.05 mol, preferably 0.98 to 1.02 mol.

  In addition, you may add components, such as dicarboxylic acids, such as phthalic anhydride, and monoamines, such as aniline, as a molecular weight regulator to the said reaction system. In this case, the addition amount is preferably 2 mol% or less with respect to the total number of moles of the components (x) and (y).

  The conditions for the single-stage polymerization method are a reaction temperature of 150 to 300 ° C. and a reaction time of about 1 to 15 hours. In addition, as a condition in the case of the two-stage polymerization method, the polyamic acid synthesis step is performed at a reaction temperature of 0 to 120 ° C. and a reaction time of about 1 to 100 hours, and then the obtained polyamic acid solution is usually used. The polyimide resin solution can be obtained by raising the temperature to a temperature range of 80 to 200 ° C., preferably 140 to 180 ° C., and allowing the dehydration ring-closing reaction to proceed for 1 to 15 hours. Further, a method of adding and mixing a mixed solution of acetic anhydride and pyridine to the polyamic acid solution and then raising the temperature to about 50 ° C. to perform dehydration ring closure can be employed.

  When a solvent is used in the preparation of the above (A) polyimide silicone resin, the solvent may be any one that is compatible with the components (x) and (y) that are raw materials. Examples of this solvent include phenols such as phenol, 4-methoxyphenol, 2,6-dimethylphenol, and m-cresol; ethers such as tetrahydrofuran and anisole; cyclohexanone, 2-butanone, methyl isobutyl ketone, and 2-heptanone. Ketones such as 2-octanone and acetophenone; esters such as butyl acetate, methyl benzoate and γ-butyrolactone; cellsolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; N, N-dimethylformamide, N, Examples thereof include amides such as N-dimethylacetamide and N-methyl-2-pyrrolidone. These solvents can be used singly or in combination of two or more.

  In addition, by using each of the exemplified solvents together with aromatic hydrocarbons such as toluene and xylene, it is possible to facilitate removal of water produced during dehydration ring closure by azeotropic distillation.

  Even when two or more of the tetracarboxylic acid component (x) and the diamine compound (y) are used, the reaction method is not particularly limited. For example, all reaction raw materials It may be a method in which all are charged in advance and mixed before polymerization, or a method in which two or more kinds of reaction raw materials are individually and sequentially added to the reaction system for polymerization.

As described above, the polyimide silicone resin of component (A) obtained by the above reaction is represented by the repeating unit (a), the repeating unit (b), and optionally the repeating unit (c) represented by the following formula (1). It is composed.

In the above formula, X is a tetracarboxylic acid residue derived from the component (x), for example, a tetravalent group shown below.

（式中、Ａは上記一般式（５）に関して定義のとおりである。） In the above formula, Y is a diamine residue derived from the component (y1), for example, a divalent group represented by the following general formula (2).

(In the formula, A is as defined for the general formula (5)).

（式中、Ｒ及びａは、上記一般式（６）に関して定義のとおりである。） In the above formula, Z is a diamine residue derived from the component (y2), for example, a divalent group represented by the following general formula (3).

(In the formula, R and a are as defined for the general formula (6)).

（式中、Ｂは上記一般式（７）に関して定義のとおりである。） In the above formula, W is a diamine residue derived from the component (y3), for example, a divalent group represented by the following general formula (4).

(In the formula, B is as defined for the general formula (7)).

  The content ratio of the repeating units (a), (b), and (c) contained in the polyimide silicone resin as the component (A) is substantially the same as the use ratio of the diamine compound as the components (y1) to (y3). It is.

[(B) Epoxy resin]
The epoxy resin of the component (B) of the composition of the present invention is a curable resin component, which reacts with the phenolic hydroxyl group that the component (A) has in its structure, together with the component (A). It is a component that gives a cured product together.

  The component (B) epoxy resin may be a compound having two or more epoxy groups in one molecule. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin; bisphenol A type epoxy resin such as diglycidyl bisphenol A; bisphenol F type epoxy resin such as diglycidyl bisphenol F; triphenylalkane type such as triphenylpropane triglycidyl ether Epoxy resins; cycloaliphatic epoxy resins such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; glycidyl ester resins such as diglycidyl phthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate; bis [diglycidyl Aminophenyl] methane, triglycidyl-p-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylbisua Glycidyl amine resins Roh and methyl cyclohexane. These can be used singly or in combination of two or more.

  The blending amount of the epoxy resin as the component (B) is preferably an amount that does not decrease the strength of the cured product of the composition of the present invention, and is usually 0.1-30 with respect to 100 parts by mass of the component (A). It is good to set it as the range of a mass part, Preferably it is 5-20 mass parts.

<Curing accelerator>
In the composition of the present invention, various curing accelerators may be used as necessary in order to accelerate the curing reaction of the epoxy resin as the component (B).

  Examples of the curing accelerator include organic phosphine compounds such as triphenylphosphine and tricyclohexylphosphine; trimethylhexamethylenediamine, diaminodiphenylmethane, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl). ) Amino compounds such as phenol and triethanolamine; imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole. These can be used singly or in combination of two or more. Among these, 2,4,6-tris (dimethylaminomethyl) phenol and 2-methylimidazole are preferable.

  When using the said hardening accelerator, the compounding quantity is 10 mass parts or less normally with respect to 100 mass parts of total amounts of the said (A) component and (B) component, Preferably, it is 0-5 mass parts. is there. When there are too many said compounding quantities, the pot life of this invention composition may become short and it may be inferior to workability | operativity.

[(C) Conductive metal powder]
The conductive metal powder which is the component (C) of the composition of the present invention is blended to impart conductivity to the cured product obtained from the composition of the present invention and to apply the composition of the present invention as a conductive adhesive. It is an ingredient.
Examples of the conductive metal powder of component (C) include metal powders such as silver, gold, copper, and nickel.

  Among these, silver powder is particularly preferably used because of its excellent electrical characteristics, thermal conductivity, and oxidation resistance performance. The shape of the silver powder is not particularly limited, and may be, for example, a granular shape, a dendritic shape, a flake shape, an indefinite shape, or a combination of silver powders having different shapes. The particle size of the silver powder is not particularly limited, but is usually 0.05 to 100 μm, preferably within the range of 0.1 to 50 μm. The average particle size is usually in the range of 1 to 10 μm, preferably 2 to 8 μm. The shape, particle size, and average particle size of the silver powder are as follows, so that the tap density is high and the specific surface area (the same applies to the BET method hereinafter) is small. It is preferable because it can be highly filled into the product. In addition, the said particle size is a laser diffraction diameter, and is a value measured by dispersing a silver powder in isopropyl alcohol and using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

Aggregates between silver powders and is an indicator of the properties that can be present in a high density and high filling by being uniformly dispersed in the matrix phase (A), (B), etc. Is mentioned. The tap density of the silver powder used in the present invention is usually, 3.0 g / cm ³ or more, preferably 4.0~7.0g / cm ^3, more preferably a 5.0~6.5g / cm ^3. The specific surface area is usually, 2.0 m ² / g or less, preferably 0.05 to 1.0 m ² / g, more preferably 0.1~0.7m ² / g.
The method for measuring the tap density of the silver powder in the present invention is as described later.

  If the tap density of the silver powder is too low, it will be difficult to disperse silver with high density in the cured product of the composition of the present invention, and the thermal conductivity of the cured product will decrease. If the specific surface area of the silver powder is too large, the amount of the organic solvent used increases when the organic solvent is added to the composition of the present invention to form a paste, and the remaining organic solvent accompanying the silver powder further increases. Due to the increased amount, the conductive properties are reduced when applied as a conductive adhesive.

  Although the manufacturing method of the silver powder used by this invention is not specifically limited, For example, the electrolytic method, the grinding | pulverization method, the heat processing method, the atomizing method, the reduction method etc. are mentioned. Among these, the reduction method is preferable because a powder having a high tap density and a small BET specific surface area can be easily obtained by controlling the reduction method.

  In addition, you may grind | pulverize and use silver powder in the range with which the preferable numerical range which concerns on said tap density and specific surface area is satisfy | filled. The apparatus in the case of grind | pulverizing silver powder is not specifically limited, For example, well-known apparatuses, such as a stamp mill, a ball mill, a vibration mill, a hammer mill, a rolling roller, a mortar, are mentioned.

  The blending amount of the conductive metal powder of component (C) is usually 400 to 3,000 parts by mass with respect to 100 parts by mass of component (A) in order to improve the conductivity and workability. The amount is preferably 500 to 2,500 parts by mass.

[(D) Silica]
Silica which is (D) component of this invention composition is a component mix | blended in order to provide thixotropy to this invention composition, and to suppress stringing and a spreading | diffusion at the time of application | coating. The surface of silica may be hydrophilic or hydrophobic, but silane or silicone-treated silica is preferable. The finer the particle size, the better the thixotropy can be imparted. Moreover, 1-100 mass parts is good with respect to 100 mass parts of (A) component, and, as for the quantity of the silica to mix | blend, Preferably it is 10-50 mass parts. If it is less than this range, the desired thixotropy will not be exhibited, and if it is more than this range, the features of conductivity and adhesiveness will be impaired.

The BET specific surface area of silica is preferably 50 to 400 m ² / g, and the average primary particle diameter is preferably 5 to 40 nm. Specifically, Aerosil series of Japan Aerosil Co., Ltd. (Aerosil R972, Aerosil R974, Aerosil R9200, Aerosil R976, Aerosil R976S, Aerosil RX50, Aerosil NAX50, Aerosil NX90, Aerosil RX200, Aerosil RX8200, Aerosil RX8, Aerosil R812S, Aerosil RY50, Aerosil NY50, Aerosil RY200S, Aerosil R202, Aerosil RY200, Aerosil RY300, Aerosil R104, Aerosil R106, Aerosil NA50H, Aerosil NA50Y, Aerosil RA200H, Aerosil NA200R, Aerosil NA200R, Aerosil NA200R 50, Aerosil R711, Aerosil R7200, Aerosil OX50, Aerosil 50, Aerosil 90G, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 300, Aerosil 380, etc.) and Tokuyama's QS102, MT10, DM10, DM20S, DM30, DM30S , KS20S, KS30S, HM20S, PM20, PM20S, ZD30S and the like.

[Other ingredients]
In addition to the above-described components, it is optional to add other components to the composition of the present invention as necessary within a range not impairing the object and effect of the present invention.

<Adhesion improver>
A monofunctional epoxy compound containing one epoxy group in one molecule and carbon functional silane may be added for the purpose of improving adhesion to the substrate. Examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. These can be used singly or in combination of two or more. When using this component, the compounding quantity is about 0.5-2.0 mass parts normally with respect to 100 mass parts of said (A) component.

<Conductive material>
Moreover, electroconductive materials other than the said (C) component can be mix | blended.
Examples of the conductive material include conductive carbon black, conductive zinc white, and white conductive titanium oxide.

  As the conductive carbon black, those commonly used for conductive rubber compositions can be used. For example, acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), extra conductive Furnace Black (XCF), Conductive Channel Black (CC), Furnace Black and Channel Black heat-treated at a high temperature of about 1,500 ° C. can be exemplified.

  Specifically, for example, acetylene black such as electrified acetylene black (trade name, manufactured by Electrochemical Co., Ltd.), Shaunigan acetylene black (trade name, manufactured by Shaunigan Chemical Co., Ltd.); Continex CF (trade name, Continental Carbon) , Vulcan C (trade name, manufactured by Cabot), etc .; Super-Conductive Furnace Black, such as Continex SCF (trade name, manufactured by Continental Carbon), Vulcan SC (trade name, manufactured by Cabot); Asahi HS-500 (trade name, manufactured by Asahi Carbon Co., Ltd.), Vulcan XC-72 (trade name, manufactured by Cabot Corp.) and other extra conductive furnace blacks; Kolux L (trade name, manufactured by Degussa Corp.) and other conductive channel blacks Named, also fur Is one of the scan black Ketchen Black EC (trade name, manufactured by Ketchen Black International Co., Ltd.), it can also be used Ketchen black EC-600JD (same).

Among these, acetylene black is particularly preferably used in the present invention because it has a low impurity content, has a developed secondary structure, and is excellent in conductivity.
Further, the above-described ketjen black EC, ketjen black EC-600JD, etc., which have an extremely large specific surface area and exhibit excellent conductivity even at a low blending amount, can be preferably used.

Examples of white conductive titanium oxide include ET-500W (trade name, manufactured by Ishihara Sangyo Co., Ltd.). In this case, the basic composition is preferably TiO ₂ · SnO ₂ doped with Sb.

These conductive materials can be used singly or in combination of two or more.
When using this electroconductive material, the compounding quantity is 1-500 mass parts normally with respect to 100 mass parts of said (A) component, Preferably it is about 2-300 mass parts.

<(E) Organic solvent>
In order to dilute and uniformly mix each of the above components, and to improve workability in application as a conductive adhesive, the composition of the present invention may contain (E) an organic solvent. it can.
The component (E) is preferably compatible with the components (A) and (B) and not reactive with the component (B).

Specific examples of the component (E) include ethers such as tetrahydrofuran and anisole; ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone; n-butylcarbi Esters such as tall acetate, butyl acetate, methyl benzoate, and γ-butyrolactone; cellosolves such as butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether, tripropylene glycol nbutyl ether, and polyethylene glycol dimethyl ether; N, N— Examples include amides such as dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; and aromatic hydrocarbons such as toluene and xylene. These can be used singly or in combination of two or more.
Among the above, ketones, esters and cellosolves are preferable, and n-butyl carbitol acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone are particularly preferable.

  The blending amount of the organic solvent of the component (E) is set in consideration of the solubility of the resin component, the workability of the application process to the substrate, the thickness of the predetermined film, etc. The amount is usually 50 to 1,000 parts by mass, preferably 100 to 600 parts by mass with respect to 100 parts by mass of the component. In the storage, transportation and the like of the composition of the present invention, for example, the component (E) is not blended or only a small amount thereof is added to make the concentration of the resin component relatively high, and the coating step. For example, a sufficient amount of component (E) may be added to dilute to a predetermined concentration.

[Conductive adhesive]
The composition of the present invention can be suitably used particularly as a conductive adhesive. Specifically, this conductive adhesive is used for applications such as IC die bonding, LCD upper and lower electrode bonding, bare chip mounting, TAB electrode bonding, LED chip or LD chip bonding to a lead frame, and the like. Can be applied.

  The conductive adhesive is usually preferably in the form of a paste, a high-viscosity liquid, or a liquid that can be applied with a screen printing method. In order to obtain these predetermined forms, it can be designed mainly by adjusting the blending ratio of the components (A) to (D), blending a predetermined amount of the component (E), and the like.

  As a method for applying the conductive adhesive, generally, a step of forming an adhesive layer by coating, potting or dipping on the surface of an adherend (ie, a substrate), and then applying an adhesive member to the adhesive layer. The step of pressure bonding and the step of evaporating and curing the volatile component such as the component (E) in the adhesive layer by processing at a predetermined temperature and time condition thereafter are included. In the step of forming the adhesive layer, an adhesive layer having a thickness of about 5 to 50 μm is usually formed depending on the intended performance.

  In the step of curing the adhesive layer, the curing conditions vary depending on the types and amounts of the components (A) and (B) and whether or not the curing accelerator is used, and are not particularly limited. However, it is usually at a temperature in the range of 80 to 300 ° C., preferably 100 to 250 ° C., for about 10 to 120 minutes. If the temperature is too low, the time required for curing becomes long, which is not practical. Conversely, if the temperature is too high, the adhesive member may be deteriorated. In addition, since the adhesive of this invention uses the polyimide silicone resin by which the ring cyclization was carried out beforehand as (A) component, compared with the case where an adhesive agent contains a polyamic acid, it requires for the cyclization of a polyamic acid. For example, there is an advantage that the high temperature condition exceeding 300 ° C. is not required.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

<Measuring method of tap density of silver powder>
First, 100 g of silver powder is weighed and gently dropped into a graduated cylinder (diameter: 22 mm, capacity: 100 ml) using a funnel. This graduated cylinder is set in a tap density measuring device (manufactured by Kodaira Seisakusho), and after tapping 600 times at a drop distance of 20 mm and at intervals of 1 second, the volume of the compressed silver powder is measured. The tap density was calculated and obtained.

<Viscosity measurement method>
Measurement was performed at a sample temperature of 25 ° C. using an EHD viscometer.

で表されるジアミノシロキサン３５ｇ（０．０４モル）、（ｙ１）３，３’−ジヒドロキシ−４，４’−ジアミノビフェニル１７．４ｇ（０．０８モル）及び（ｙ３）２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン３２．８ｇ（０．０８モル）を、Ｎ−メチル−２−ピロリドン１００ｇに溶解させた溶液を、反応系の温度が５０℃を超えないように調節しながら、上記フラスコ内に滴下した。 [Preparation Example 1]
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, (x) 4,4′-hexafluoropropylidenebisphthalic dianhydride 88.2 g (0.2 mol) and N-methyl-2- 400 g of pyrrolidone was charged.
Next, (y2) the following structural formula:

Diaminosiloxane represented by formula (35) (0.04 mol), (y1) 3,3′-dihydroxy-4,4′-diaminobiphenyl 17.4 g (0.08 mol) and (y3) 2,2-bis [ A solution prepared by dissolving 32.8 g (0.08 mol) of 4- (4-aminophenoxy) phenyl] propane in 100 g of N-methyl-2-pyrrolidone was adjusted so that the temperature of the reaction system did not exceed 50 ° C. Then, it was dropped into the flask.

After completion of dropping, the mixture was further stirred at room temperature for 10 hours. Next, after attaching a reflux condenser with a moisture receiver to the flask, 50 g of xylene was added, the temperature was raised to 150 ° C. and the temperature was maintained for 6 hours, and a yellowish brown solution was obtained.
The yellow-brown solution thus obtained was cooled to 25 ° C. and then poured into methanol for precipitation. Subsequently, it filtered and the obtained solid content was dried and the reaction product was obtained. This is designated as polyimide silicone resin (I). The weight average molecular weight (in terms of polystyrene) of this resin measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 30,000.

[Preparation Example 2]
The amount of diaminosiloxane used as the component (y2) described in Preparation Example 1 was changed from 35 g (0.04 mol) to 70 g (0.08 mol), and 2,2-bis [ Polyimide silicone resin in the same manner as in Preparation Example 1, except that the amount of 4- (4-aminophenoxy) phenyl] propane used was changed from 32.8 g (0.08 mol) to 16.4 g (0.04 mol). (II) was obtained. The weight average molecular weight (in terms of polystyrene) of this resin measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 33,000.

[Example 1]
(A1) 100 parts by mass of the polyimide silicone resin (I) obtained in Preparation Example 1, 18 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 20 Pa · s) was obtained. Next, this solution was treated with 900 parts by mass of silver powder having an average particle size of 2.9 μm, a tap density of 5.70 g / cm ³ and a specific surface area (BET method) of 0.42 m ² / g and dimethylsiloxane. 40 parts by mass of silica having a specific surface area of 130 m ² / g (Aerosil RY200S, manufactured by Nippon Aerosil Co., Ltd.) is added, and 120 parts by mass of n-butyl carbitol acetate is added and dispersed uniformly to obtain an off-white paste. Composition (viscosity at 25 ° C .: 100 Pa · s) was obtained. This is designated as conductive adhesive A.

[Example 2]
(A1) 100 parts by mass of the polyimide silicone resin (I) obtained in Preparation Example 1, 18 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 20 Pa · s) was obtained. Next, this solution was treated with 900 parts by mass of silver powder having an average particle diameter of 2.9 μm, a tap density of 5.70 g / cm ³ and a specific surface area (BET method) of 0.42 m ² / g and dimethylsilane. 40 parts by mass of silica having a specific surface area of 130 m ² / g (Aerosil RY200S, manufactured by Nippon Aerosil Co., Ltd.) was added, and 110 parts by mass of n-butyl carbitol acetate was added as needed to stir and uniformly disperse, giving an off-white paste Composition (viscosity at 25 ° C .: 100 Pa · s) was obtained. This is referred to as conductive adhesive B.

[Example 3]
(A2) 100 parts by mass of the polyimide silicone resin (II) obtained in Preparation Example 2 above, 15 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 25 Pa · s) was obtained. Next, 1,900 parts by mass of silver powder having an average particle diameter of 3.7 μm, a tap density of 5.50 g / cm ³ and a specific surface area (BET method) of 0.32 m ² / g and dimethylsiloxane 40 parts by mass of treated silica having a specific surface area of 130 m ² / g (Aerosil RY200S, manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was stirred and uniformly dispersed while appropriately adding 130 parts by mass of n-butyl carbitol acetate. A paste-like composition (viscosity at 25 ° C .: 90 Pa · s) was obtained. This is designated as conductive adhesive C.

[Comparative Example 1]
(A1) 100 parts by mass of the polyimide silicone resin (I) obtained in Preparation Example 1, 18 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 20 Pa · s) was obtained. Next, 900 parts by mass of silver powder having an average particle diameter of 2.9 μm, a tap density of 5.70 g / cm ³ , and a specific surface area (BET method) of 0.42 m ² / g is added to this solution and stirred. It was uniformly dispersed to obtain a grayish white paste-like composition (viscosity at 25 ° C .: 100 Pa · s). This is designated as conductive adhesive D.

[Comparative Example 2]
(A1) 100 parts by mass of the polyimide silicone resin (I) obtained in Preparation Example 1, 18 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 20 Pa · s) was obtained. Next, in this solution, 900 parts by mass of silver powder having an average particle diameter of 2.9 μm, a tap density of 5.70 g / cm ³ and a specific surface area (BET method) of 0.42 m ² / g and n-butyl carbitol. 120 parts by mass of acetate was added, stirred and uniformly dispersed to obtain a grayish white paste-like composition (viscosity at 25 ° C .: 10 Pa · s). This is designated as conductive adhesive E.

[Comparative Example 3]
(A2) 100 parts by mass of the polyimide silicone resin (II) obtained in Preparation Example 2 above, 15 parts by mass of diglycidyl toluidine, and 230 parts by mass of n-butyl carbitol acetate are put into a milk beak and kneaded. A fluid solution (viscosity at 25 ° C .: 25 Pa · s) was obtained. Next, 1,900 parts by mass of silver powder having an average particle diameter of 3.7 μm, a tap density of 5.50 g / cm ³ , and a specific surface area (BET method) of 0.32 m ² / g was added to this solution, The mixture was stirred and dispersed uniformly to obtain an off-white paste composition (viscosity at 25 ° C .: 90 Pa · s). This is designated as conductive adhesive F.

[Comparative Examples 4 and 5]
As Comparative Example 4, a commercially available high heat-resistant epoxy-based conductive adhesive (trade name: Sylbest P-2460, manufactured by Tokiki Chemical Laboratory Co., Ltd.) is used. This is designated as conductive adhesive G.
As Comparative Example 5, a commercially available silicone-based conductive adhesive (trade name: Sylbest P-2457, manufactured by Tokuru Chemical Laboratory Co., Ltd.) is used. This is designated as conductive adhesive H.

<Performance evaluation test method>
For each of the above conductive adhesives, the specific resistance, adhesive strength and thermal conductivity were measured as follows. As for the spreadability at the time of application, an adhesive is applied on the Si substrate with the tip of the toothpick applied, and the range in which the adhesive is applied after 10 minutes compared to the range of the adhesive immediately after the application is 10 If it was larger than%, it was marked as ○ if it was within 10%. Regarding the stringing at the time of application, the toothpick was put into the container containing the adhesive from the beginning, and when the adhesive was lifted slowly by 1 cm or more, it was evaluated as x.

Specific resistance:
Each of the conductive adhesives was printed on a slide glass with a pattern of 5 mm × 10 mm by a screen printing method, and then treated under conditions of 180 ° C. × 1 hour to cure the adhesive layer. The thickness of the hardened layer was measured, and further, the electrodes were in contact with both ends in the longitudinal direction of the pattern, and the electrical resistance was measured. The specific resistance was calculated based on the measurement result.
Moreover, the hardened layer produced | generated on the said slide glass was heat-processed on the conditions of 150 degreeC x 2,000 hours, and the specific resistance was calculated | required like the above about the thing after this heat processing.

Adhesive strength:
Each conductive adhesive was applied to a thickness of 10 μm on a 25 mm × 25 mm copper plate.
On this adhesive layer, a brass piece having a bottom of 2.8 mm × 2.5 mm (area: 7 mm ² ) and a height of 7 mm was stacked and pressure-bonded. Next, the adhesive layer was cured by heat treatment under conditions of 180 ° C. × 1 hour.
Using the test specimen thus obtained, a push-pull gauge was brought into contact with a position 1 mm high from the bottom of the 7 mm-high brass piece and pushed until the brass piece peeled off from the copper plate and fell down. The maximum value displayed on the push-pull gauge was read, and the adhesive strength (N / 7 mm ² ) was measured.
Moreover, the said test body was heat-processed on the conditions of 150 degreeC x 2,000 hours, and the adhesive strength was measured like the above about the thing after this heat processing.

Thermal conductivity:
Each conductive adhesive is poured into a cylindrical hole of a Teflon (registered trademark, trade name, manufactured by DuPont) plate, heat-treated under conditions of 180 ° C. × 1 hour, cured, and tested with a diameter of 10 mm × 1 mm. A piece was made. About this test piece, the thermal diffusivity and specific heat capacity were measured using the laser flash method thermal constant measuring apparatus (made by ULVAC-RIKO), and the thermal conductivity (W / m * K) was calculated | required from the measurement result.
The above measurement results are shown in Table 2.

[Evaluation]
(1) It turns out that the conductive adhesives A, B, and C which are Examples are excellent in applicability compared with the conductive adhesives D, E and F using polyimide silicone as a binder.
(2) The conductive adhesives A, B, and C which are examples show a specific resistance value lower than that of the conductive adhesive G of the comparative example, and the change rate after the heat resistance durability test is small, It can be seen that the rate of change of the adhesive strength after the heat resistance durability test is small, and a cured film having high thermal conductivity is formed.
(3) The conductive adhesives A, B, and C, which are examples, show a larger adhesive strength than the conductive adhesive H of the comparative example, the change rate after the heat and durability test is small, and high heat conduction It turns out that the cured film which has property is formed.

  From the above results, the composition of the present invention is excellent in application property, conductivity, adhesiveness, thermal conductivity and heat resistance as a conductive adhesive, and excellent in durability with little deterioration in performance even after long-term use. It can be seen that When the conductive adhesive is used for bonding the LED chip of a high-luminance LED component for lighting and a lead frame, the initial performance is sufficiently sufficient for heat generation due to long-time continuous use of the LED component. It can be maintained.

Claims (8)

(A) The following formula (1):

[Wherein, X is a tetracarboxylic acid residue derived from a tetracarboxylic acid component, and Y is the following general formula (2):

(In the formula, A is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, or —SO ₂ —).
When a plurality of A are present in the molecule of the component (A), these A are the same or different, and Z is the following general formula (3):

(In the formula, R is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 1 to 120.)
W is a diamine residue derived from a diamine compound other than a diamine compound having two or more phenolic hydroxyl groups and a diamine compound having a siloxane structure. p is 10 to 80 mol%, q is 5 to 50 mol%, r is 0 to 50 mol%, and p + q + r is a number that is 100 mol%. ]
Represented by: a polyimide silicone resin composed of a repeating unit (a), a repeating unit (b), and optionally a repeating unit (c) and having two or more phenolic hydroxyl groups in one molecule;
(B) epoxy resin,
(C) conductive metal powder,
A curable resin composition comprising (D) silica and (E) an organic solvent.   In the component (A), the content p of the repeating unit (a) is 10 to 80 mol%, the content q of the repeating unit (b) is 5 to 50 mol%, and the repeating unit (c The curable resin composition according to claim 1, wherein a content ratio r of 1) to 50 mol% is provided, wherein the total content ratio of the repeating units (a) to (c) is 100 mol%. W is the following general formula (4):

(Where B is

When a plurality of B are present in the molecule of the component (A), these B are the same or different. )
The curable resin composition according to claim 1, which is a divalent group represented by the formula:   The curable resin composition according to claim 1, wherein the component (C) is silver powder.   100 parts by weight of the (A) component, 0.1-30 parts by weight of the (B) component, 400-3,000 parts by weight of the (C) component, 1-100 parts by weight of the (D) component, The curable resin composition according to any one of claims 1 to 4, comprising 50 to 1,000 parts by mass of the component (E).   The curable resin composition according to any one of claims 1 to 5, wherein the curable resin composition is used for producing a high-intensity light-emitting diode component.   The curable resin composition according to claim 6, which is used for bonding a Zener diode and a lead frame used in an LED chip and a lead frame or an LED package.   The electroconductive adhesive agent containing the curable resin composition of any one of Claims 1-7.