JPH1180695A - Resin composition and electric-conductive adhesive therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which gives a cured material which is flexible even if a large amount of filler such as a metal powder and the like is mixed and the flexibility of which material does not change by heat or the like and to provide an electric-conductive adhesive having an excellent flexibility, an excellent heat resistance and an excellent conductivity. SOLUTION: A resin compound comprises (A) a polymer compound containing hydroxide groups having a main chain structure in which preferably a 4-10C alkyl group is contained between ester bonds or ether bonds and containing hydroxide groups at the both end of the molecule, (B) an epoxy compound having the same main chain structure, alicyclic epoxy groups at the both end of the molecule and an epoxy equivalent of not less than 480, (C) a silane compound having hydroxide or alkoxyl groups bonding to silicon atoms and (D) a chelating compound such as an aluminum chelating compound and the like. A conductive adhesive comprises 5-30 wt.% of said resin compound and 95-70 wt.% of a conductive filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition which can be used as a resin component of a conductive adhesive, and a conductive adhesive using the resin composition. More specifically, a resin composition for a conductive adhesive which is particularly suitable for joining a crystal resonator or a ceramic resonator constituting a resonator component to a lead wire or the like, and a conductive composition using this resin composition For adhesives.

[0002]

2. Description of the Related Art Conventionally, various kinds of vibrators such as a crystal vibrator and a ceramic vibrator constituting a vibrator part are electrically connected to a lead wire or the like by using a conductive filler such as silver powder in a synthetic resin. Dispersed conductive adhesives have been used, and flexible materials such as polyurethane, silicone, and epoxy have been used as resin components of these conductive adhesives. However, the conductive adhesive using a silicone resin has a drawback that the silicone resin is hardly cured by the inclusion of a conductive filler such as silver, and it is difficult to obtain a stable cured product. Further, there is a disadvantage that low-molecular components in the silicone resin are volatilized and condensed on the substrate to easily cause poor conduction at the contact portion.

Further, a conductive adhesive using a urethane resin has a disadvantage in that the heat resistance of the resin is poor, so that when the electronic equipment is placed at a high temperature, the resin deteriorates with time and the resin becomes hard. In particular, in the joining of the vibrators, there are disadvantages that the vibration characteristics of the vibrator are changed and the vibrator is easily dropped from the lead wire.

On the other hand, epoxy resin has high mechanical strength and excellent heat resistance, and is suitable as a resin component for a conductive adhesive. However, a large amount of conductive filler is mixed with the resin. However, in such a formulation, the cured product loses flexibility, and there is a drawback that the flexibility required particularly for joining the vibrator cannot be obtained.

[0005] The above disadvantages of the epoxy resin can be improved by adding a flexibility-imparting component to the epoxy resin and modifying the epoxy resin. Examples of the flexibility-imparting component include a hydroxyl-containing polymer compound. The curing reaction between the hydroxyl-containing polymer compound and the epoxy resin is described in
No. 73825.

According to the above publication, a number-average 3000 to 200,000 hydroxyl-containing polymer compound having an average of two or more hydroxyl groups in one molecule is added, and this is added to one molecule in one molecule on average.
More than one alkoxysilane group, silanol group, silane compound having a functional group such as an acyloxysilane group, and aluminum, titanium, by reacting in the presence of a curing catalyst comprising a metal chelate compound such as zirconium, for coating applications. It has been shown that a suitable resin composition can be obtained.

The hydroxyl group-containing polymer compound in the resin composition includes an acrylic polyol polymer compound, a polyester polyol polymer compound, a fluorine polyol polymer compound, a polyurethane polyol polymer compound,
Silicone polyol polymer compounds and vinyl alcohol-styrene copolymers are mentioned, but the flexibility obtained by these hydroxyl group-containing polymer compounds is such that the resin contains a large amount of conductive fillers and still has a flexible cured product. It is not sufficient for the purpose to be obtained. In particular, in the case of the above-mentioned acrylic polyol polymer compound, fluorine polyol polymer compound, polyurethane polyol polymer compound, vinyl alcohol-styrene copolymer, the effect of imparting flexibility is relatively small, and therefore, in the cured conductive adhesive, However, there is a problem that flexibility is insufficient.

Further, since the silicone polyol polymer compound is a non-polar compound, it is difficult to mix uniformly with an epoxy compound having a relatively high polarity, and it is difficult to obtain a uniform cured product. Was.

In this regard, the polyester polyol polymer compound has a high flexibility-imparting effect and can be used as a flexible epoxy resin. However, when a conductive adhesive is added to form a conductive adhesive, flexibility is increased. And is no longer suitable as an adhesive for transducer parts. In addition, when an aliphatic polymer compound is used as the polyester polyol, an excellent flexibility-imparting effect can be expected, but a generally used catalyst is inferior in reactivity with the epoxy resin, and a cured product is obtained. Even so, there is a problem that a change in hardness with time is large.

[0010]

Accordingly, the present invention has a flexibility particularly suitable for joining a vibrator and can maintain the flexibility stably for a long period of time.
It is an object of the present invention to provide a resin composition capable of obtaining a conductive adhesive which does not adversely affect the vibration characteristics of the joined vibrator and a conductive adhesive using the resin composition.

[0011]

Means for Solving the Problems In order to achieve the above object, the resin composition of the present invention is an aliphatic compound having a molecular skeleton constituting a main chain and containing a polyester unit or a polyether unit and having a molecular weight of 1,000 or more. A hydroxyl group-containing polymer compound (A) having 4 or more carbon atoms in the polyester unit or the polyether unit except for those included in the functional group, and having hydroxyl groups at both molecular ends, and a molecule constituting a main chain. The skeleton is an aliphatic compound containing a polyester unit or a polyether unit, and the number of carbon atoms of the polyester unit or the polyether unit is 4 or more except those included in the functional group, and an alicyclic compound is provided at both ends of the molecule. An epoxy compound (B) having an epoxy group and having an epoxy equivalent of 480 or more, a hydroxyl group or an alkoxy group bonded to Si in one molecule. Silane compound having at least one group (C), aluminum chelate compounds are characterized by containing at least one chelate compound selected from a titanium chelate compound and zirconium chelate compound (D).

In this resin composition, the hydroxyl-containing polymer compound (A) is added to the total amount of the hydroxyl-containing polymer compound (A) and the epoxy compound (B).
Is 30 to 85% by weight and the epoxy compound (B) is 70 to 1%.
It is preferable that the silane compound (C) is mixed at a ratio of 5% by weight.
And 100 parts by weight of the epoxy compound (B)
It is preferably contained in a proportion of 5 parts by weight or less,
In particular, it is preferable that the blocked isocyanate compound is further added at a ratio of 2 to 25 parts by weight based on 100 parts by weight of the epoxy compound (B).

Further, the conductive adhesive provided by the present invention is characterized by comprising 5 to 30% by weight of the above resin composition and 95 to 70% by weight of the conductive filler.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The hydroxyl group-containing polymer compound (A) used in the present invention has a molecular weight of 1 containing a polyester unit or a polyether unit in the molecular skeleton constituting the main chain.
000 or more aliphatic compounds, and the number of carbon atoms of the polyester unit or the polyether unit is 4 or more, preferably 4 to 10, excluding those included in the functional group, and a hydroxyl group is provided at both ends of the molecule. Compounds. The functional group is an ester bond, an ether bond, or the like.
When the number of hydroxyl groups contained in one molecule of the hydroxyl group-containing polymer compound (A) is 3 or more, the crosslink density becomes too large, and the cured product of the resin composition is inferior in flexibility. Further, as the hydroxyl group-containing polymer compound (A), a condensate of an aliphatic diol having 4 or more carbon atoms in the main chain and an aliphatic dicarboquinic acid compound having 6 or more carbon atoms in the main chain and having a molecular weight of 1000 or more Can be used. When a hydroxyl group-containing polymer compound having less than 4 carbon atoms between ester bonds or ether bonds or a hydroxyl group-containing polymer compound containing an aromatic ring in the main chain is used, a cured resin composition or a conductive adhesive is obtained. Poor flexibility. When the molecular weight is less than 1,000, the flexibility of the cured product is insufficient. If the molecular weight exceeds 100,000, the cured product tends to become brittle. When the hydroxyl group-containing polymer compound (A) has hydroxyl groups at both molecular terminals, a cured product excellent in curing reactivity and excellent in flexibility is easily obtained.

Examples of such diols include divalent acids (eg, adipic acid, sebacic acid) and divalent diols (eg, butanediol, hexamethylene glycol, 3-methyl-1,5-pentanediol) A) a polyester diol obtained by a condensation reaction with
Diols comprising four or more aliphatic carbons between ether oxygens (for example, oxetane polymers, lactone ring-opening polymers having hydroxyl groups at the molecular terminals) can be mentioned.

Epoxy compound (B) usable in the present invention
Is an aliphatic compound in which the molecular skeleton constituting the main chain contains a polyester unit or a polyether unit, and the number of carbon atoms of the polyester unit or the polyether unit is not less than 4 except for those included in the functional group, preferably Is 4 ~
Ten, having an alicyclic epoxy group at both ends of the molecule,
It is a compound having an epoxy equivalent of 480 or more. When the epoxy compound (B) has alicyclic epoxy groups at both molecular terminals, a cured product having excellent curing reactivity and excellent flexibility is easily obtained.

In the above, when an epoxy compound having an epoxy equivalent of less than 480 or having three or more epoxy groups in one molecule is used, the crosslinked density of the cured product becomes too large and the cured product becomes flexible. Inferior.

If the epoxy compound has no aliphatic polyester or polyether component, the cured product still lacks flexibility. Preferred epoxy compounds (B) include those having an epoxycyclohexyl group at both terminals of the above diol.

The mixing ratio of the hydroxyl group-containing polymer compound (A) and the epoxy compound (B) is based on 100 parts by weight of the total of the hydroxyl group-containing polymer compound (A) and the epoxy compound (B). 30 to 85 of the polymer compound (A)
The epoxy compound (B) is preferably 70 to 15 parts by weight, and the hydroxyl group-containing polymer compound (A) is 40 to 70 parts by weight, and the epoxy compound (B) is 60 to 3 parts by weight.
Particularly preferred is 0 parts by weight. When the amount of the hydroxyl group-containing polymer compound (A) is less than 30 parts by weight (30% by weight), the cured product is inferior in flexibility. When the amount exceeds 85 parts by weight (85% by weight), the curability is inferior. Strength becomes small and is not suitable for practical use.

The silane compound (C) usable in the present invention
Is a compound having at least one hydroxyl group or alkoxy group bonded to a silicon atom (Si). The alkoxy group in the silane compound is preferably one having 1 to 6 carbon atoms, for example, methoxy, ethoxy , N-propoxy, iso-propoxy n-putoxy and the like. Specific examples of these compounds include γ-glycidoxypropylsilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and the like.

In the above silane compound, when one hydroxyl group or one alkoxy group is contained in one molecule, the catalytic activity is relatively small. Therefore, a plurality of hydroxyl groups or alkoxy groups, specifically, two or three groups, are contained in one molecule. Are preferred.
At this time, if the aluminum complex / siloxane compound has a plurality of hydroxyl groups or alkoxy groups in one molecule, the silane compounds can form a Si-O-Si bond and crosslink. However, such crosslinking increases the crosslinking density of the cured product and deteriorates the flexibility of the cured product.
It is preferable to use a silane or organosiloxane compound having at least two hydroxyl groups or alkoxy groups bonded to Si in the molecule.

The silane compound (C) is used in an amount of 15 parts by weight or less, especially 1 part by weight, based on 100 parts by weight of the total of the hydroxyl-containing polymer compound (A) and the epoxy compound (B).
Preferably, the amount is from 10 to 10 parts by weight.

The chelate compound (D) used in the present invention
Is at least one selected from an aluminum chelate compound, a titanium chelate compound and a zirconium chelate compound, and specific examples thereof include tris (acetylacetonate) aluminum, tris (ethylacetonate) aluminum, bis (acetylacetone) titanate, And tetrakis (acetylacetonate) zirconium.

The resin composition of the present invention is, for example,
In the resin composition of the present invention, the reaction between the hydroxyl-containing polymer compound (A) and the epoxy compound (B) can be carried out under a curing condition in a relatively low temperature range such as 1 hour. In general, either the hydroxyl group-containing polymer compound (A) or the epoxy compound (B) tends to remain in the cured product of the resin composition, and this residue may cause a temporal change in hardness. In order to solve the problem, it is preferable to use a blocked isocyanate in combination. Examples of the blocked isocyanate compound that can be used include a compound obtained by blocking a bifunctional isocyanate compound with phenol, ethyl acetoacetate, diethyl malonate, or the like.

The combined use of a blocked isocyanate compound
As described above, even when unreacted epoxy groups or hydroxyl groups remain after curing at a low temperature for a short time, the isocyanate compound can react and cure with these epoxy groups or hydroxyl groups to exhibit the performance as an adhesive resin. Therefore, the presence of an epoxy compound that is not completely cured by the initial reaction is effective in resolving the drawback of increasing the time-dependent change in the hardness of the cured adhesive, and the combined use of a blocked isocyanate compound reduces the required amount of the epoxy compound. Therefore, the change with time of the hardness can be reduced accordingly.
Further, since the blocked isocyanate is rich in reactivity with the epoxy compound, the curing temperature and the curing time of the resin composition of the present invention can be further reduced.

The blocked isocyanate compound is preferably added to the resin composition or the conductive adhesive in a ratio of 2 to 25 parts by weight based on 100 parts by weight of the epoxy compound (B). If the amount is less than 2%, the curability at low temperature and short time will be low, and if it exceeds 20% by weight, the heat resistance of the resin composition will be reduced, and at the same time the blocking agent for the blocked isocyanate compound or its decomposition will be decomposed. Depending on the object, there is a possibility that the characteristics of the joined parts are degraded.

The resin composition of the present invention may contain a monofunctional epoxy compound called a reactive diluent in addition to the above components. The reaction diluent is not only a viscosity modifier for the resin composition, but also can reduce the crosslink density of the cured resin, which is advantageous for softening the resin. However, since the reaction rate of the monofunctional epoxy is low, it tends to remain as an unreacted substance, and the adhesive strength is reduced accordingly, so that use of a large amount is not preferable. Generally, 10 in the resin composition
It is preferable that the proportion is in the range of 30 to 30% by weight, or the epoxy compound (B) is 40 to 75% by weight and the monofunctional epoxy compound is 60 to 25% by weight.

The resin composition of the present invention specifies the hydroxyl-containing polymer compound (A) and the epoxy compound, respectively,
Since this is combined, a cured product that is flexible and rich in flexibility even when a large amount of conductive filler is mixed, and whose flexibility does not change over a long period of time is provided. Excellent in nature. Therefore, by using the resin composition of the present invention, a conductive adhesive having excellent performance can be obtained.

The conductive adhesive of the present invention comprises the components (A) to
(D) containing the resin composition and a conductive filler, wherein the content of the resin composition is 5 to the total amount of the resin composition and the conductive filler. 30% by weight, the content of the conductive filler is 95 to 7
0% by weight. When the content of the conductive filler is less than 70% by weight, the conductivity is poor, and the content is 95% by weight.
If it exceeds, the cured product of the conductive adhesive tends to be inferior in flexibility.
The conductive adhesive of the present invention contains a large amount of a conductive filler of 95 to 70% by weight and is excellent in flexibility despite its excellent conductivity.

As the conductive filler, copper, nickel,
Examples include fine metal powders such as silver, gold, and iron, or electrically conductive fillers such as carbon powder and graphite powder. The preferred average particle size of these conductive powders is 0.1 to 20 μm.

The conductive adhesive comprises components (A) to (D)
And a conductive filler. In the conductive adhesive, components (A) to
In addition to (D), the above-mentioned reactive diluent, petroleum-based solvent and the like may be further contained.

[0032]

EXAMPLES Next, examples will be described, but the present invention is not limited by these examples. In the following examples, parts and% are parts by weight and% by weight, respectively, unless otherwise specified. Example 1 Hydroxyl group-containing polymer compound [Kuraray polyol 4010 manufactured by Kuraray Co., Ltd. (having a molecular weight of about 4000 and a main chain having four carbon atoms excluding a functional group in its repeating unit and six carbon atoms) 3-methyl- which is a diol having
10 parts of a condensate of 1,5-pentanecool having a hydroxyl group at both terminals)], an alicyclic epoxy compound [Celloxide 2 manufactured by Daicel Chemical Industries, Ltd.]
085, polycaprolactone having epoxycyclohexyl groups at both terminals and having an epoxy equivalent of 493], 10 g, silane compound [β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane], 2 parts, aluminum triacetyl 1.5 parts of acetonate was premixed with a roll mill to obtain a resin composition. And 16.3 parts of this resin composition and a conductive filler (flake silver powder,
85 parts of an average particle diameter of 8.5 μm and a petroleum solvent (SS-1)
800) and 3.8 parts, and the mixture was again kneaded with a roll mill to obtain a conductive adhesive. Further, 2.5 parts of SS-1800 was added to the conductive adhesive, and 155P
After adjusting the viscosity to (Poise, measured at 23 ° C.), this was used to test the conductive adhesive performance by the following test method.

(A) Performance test method of conductive adhesive (1) Storage stability: Put the conductive adhesive in a glass container,
It was left in a 40 ° C. constant temperature bath for 30 days, and a change in fluidity was observed. (2) Adhesive strength: A tin-plated copper wire having a diameter of 1 mm was placed on a glass plate, and the conductive adhesive was placed thereon so as to have a diameter of 5 mm, and cured at 150 ° C. for 1 hour. Thereafter, the tin-plated copper wire was pulled out at a speed of 50 mm / min, and the maximum strength (kg) at that time was defined as the adhesive strength. (3) Pencil hardness; two cellophane tapes are adhered in parallel on a glass plate at an interval of 1 cm, a conductive adhesive is placed between the cellophane tapes, and a glass rod is pulled while being pressed against the cellophane tape surface to a thickness of 15 to 20 μm. A conductive adhesive film was formed. The film was cured at 150 ° C. for 1 hour to obtain a cured product of the conductive adhesive.
5400 8.4 Pencil scratch value ", and the evaluation value was used as the initial pencil hardness. (4) Hardness change: The cured product of the conductive adhesive obtained by curing in the above (3) was further left for 1000 hours in an environment of 150 ° C., and the pencil hardness was measured in the same manner as in the above (3). ,
It was compared with the pencil hardness initial value. (5) Specific resistance; two flat electrodes were pressed at 6 cm intervals on the surface of a cured conductive adhesive obtained by curing in the same manner as in (3) above, and the resistance value between the electrodes (Ω) Was measured, and the specific resistance (Ωcm) was determined by the following equation. Specific resistance = resistance value × thickness of adhesive layer (cm) × electrode width (c
m) ÷ 6 (B) Performance test method of resin composition The resin composition (containing no conductive conductive filler) was applied on a glass plate so as to have a thickness of about 30 μm.
The resin composition was heated and cured at 50 ° C. for 1 hour to prepare a cured product of the resin composition. Next, the solvent-insoluble content and the like of the cured product were measured. (1) Solvent-insoluble matter: A cured product of the above resin composition was immersed in a mixed solvent such as toluene and methyl ethyl ketone in a beaker installed in an ultrasonic cleaner. Next, the cured product was subjected to ultrasonic cleaning with the mixed solvent for 10 minutes. After ultrasonic cleaning, determine the weight after removing the mixed solvent soluble part,
Calculate the solvent-insoluble content from the weight of the cured product before washing, and calculate
It was expressed by. That is, solvent-insoluble matter (% by weight) = 100−100 × (AB) ÷
A where A is the weight of the cured product before washing, and B is the weight of the cured product after washing.

Example 2 Hydroxyl group-containing compound [Diol PLACCEL 230 (manufactured by Daicel Chemical Industries, Ltd.) is a polycaprolactone having a molecular weight of about 3,000 and a main chain having 5 carbon atoms except for a functional group in its repeating unit; 12 parts having hydroxyl groups at both ends thereof, 8 parts of alicyclic epoxy compound (same as in Example 1), γ-methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Silicone Co., Ltd.) 1.0
Parts and 0.7 parts of aluminum triacetylacetone (manufactured by Nippon Chemical Industry Co., Ltd.) were premixed with a roll mill to obtain a resin composition. The polycaprolactone is [(CH ₂ ) ₅
COO-] _n . Here, n is a positive integer.

16.3 parts of the above resin composition, 85 parts of a conductive filler (flake silver powder, average particle size of 8.5 μm) and p-tert-butylphenyl glycidyl ether (reactive diluent, Nagase Kasei Kogyo Co., Ltd.) EX-14
6) and 3.8 parts were mixed, and the mixture was again kneaded with a roll mill to obtain a conductive adhesive. To the conductive adhesive, 2.5 parts of petroleum-based solvent SS-1800 was added, and 155P
After adjusting the viscosity to (Poise, measured at 23 ° C.), the performance was tested in the same manner as in Example 1 using this.

Example 3 In Example 1, 8 parts of celoxide 2085 were used. Instead, 6 parts of celoxide 2085 and a blocked isocyanate compound [TPLS2062 (trade name of hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.) The resin composition was prepared in the same manner as in Example 1 except that 2 parts of the resin composition was blocked with diethyl malonate, and a reactive diluent (EX-146) 5 was used.
After adding the parts (measured at a viscosity of 160 P and 23 ° C.), a conductive adhesive was prepared in the same manner as in Example 1, and their performance was similarly evaluated.

Example 4 7 parts of a hydroxyl group-containing polymer compound (Adeka polyether P-1000, polypropylene glycol having a molecular weight of about 1,000, manufactured by Asahi Denka Kogyo KK), celloxide 2085
13 parts of (epoxy compound), KBM (silane compound)
1.0 part of 503 and 0.7 part of aluminum triacetylacetone were preliminarily kneaded with a roll mill.
The silver powder (85 parts) was mixed with 6.3 parts, and the mixture was kneaded again with a roll mill to obtain a conductive adhesive. Add 4.5 parts of reactive diluent (EX-146) to the conductive adhesive.
Was added to adjust the viscosity to 160 P (23 ° C.), and the same evaluation as in Example 1 was performed using this.

Comparative Example 1 Number average molecular weight of 3 having an average of 150 hydroxyl groups in one molecule
0000 acrylic polyol (2-hydroxyethyl methacrylate / b-butyl acrylate / methyl methacrylate / azobisisobutyronitrile = 650 g /
175 g / 175 g / 10 g), 10 parts of celloxide 2085, and silane compound β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane KBM303 (manufactured by Shin-Etsu Silicon Co., Ltd.)
Using 2 parts and 1.5 parts of aluminum triacetylacetonate, a resin composition was prepared in the same manner as in Example 1, and a conductive adhesive was prepared using the resin composition. The same performance evaluation as in Example 1 was performed.

Comparative Example 2 In the composition of Example 2, as a hydroxyl-containing polymer compound, Kuraray polyol 3010 manufactured by Kuraray Co., Ltd. [molecular weight is about 3000, and the main chain has a functional group (carboxyl group) in its repeating unit. Adipic acid, a dibasic acid having 4 carbons, and a diol having 6 carbons,
Condensates with -methyl-1,5 pentanediol, having one branch in the molecule and three hydroxyl groups, one at each of the three terminals of one molecule] 10
A resin composition was obtained in the same manner as in Example 2 except for using a part, and then a conductive adhesive was prepared and the same performance evaluation was performed.

Comparative Example 3 In the composition of Example 1, instead of celloxide 2085,
Celloxide 2021 [manufactured by Daicel Chemical Industries, Ltd .; having an epoxy equivalent of 132, having no aliphatic unit between two epoxycyclohexyl groups, and having -CH ₂ -O-C
A resin composition and a conductive adhesive were prepared in the same manner as in Example 1 except that [O-bonded] was used, and their performance was evaluated.

Comparative Example 4 The procedure of Example 1 was repeated, except that bis F-type epoxy epicoat 807 manufactured by Yuka Shell Epoxy Co., Ltd. was used as the epoxy compound in place of celloxide 2085 in the composition of Example 1. , A resin composition and a conductive adhesive, and their performance was evaluated. The epoxy compound is an epoxy resin obtained by a reaction between bisphenol F and epichlorohydrin.

Comparative Example 5 In the composition of Example 1, W-100 (manufactured by Shin Nippon Rika Co., Ltd.) was used in place of celloxide 2085.
A resin composition and a conductive adhesive were obtained in the same manner as in Example 1 except that 8 parts of 6-hexanediol diglycidyl ether) were used, and their performance was evaluated.

Comparative Example 6 A conductive adhesive was prepared without using a reactive diluent in the composition of Example 4, and the viscosity was adjusted to 165P (23 ° C.) by adding 5 parts of a petroleum-based solvent (SS-1800). After that, this was evaluated in the same manner as in Example 1.

Comparative Example 7 In the composition of Example 4, polypropylene glycol (produced by Asahi Denka Kogyo KK, polypropylene glycol P-70 having a molecular weight of about 700) was used as the hydroxyl-containing polymer compound.
0) A conductive adhesive was prepared in the same manner as in Example 4 except that 7 parts were used, and the same evaluation was performed.

Table 1 summarizes the measurement results of Examples 1 to 4 and Comparative Examples 1 to 7 described above. In the storage stability column of Table 1, a circle indicates that there was no change in the fluidity after the conductive adhesive was left in a constant temperature bath at 40 ° C. for 30 days, and a cross indicates that the fluidity was not changed. Means that liquidity has been lost due to changes in

[0046]

[Table 1]

As shown in Table 1, the solvent insoluble content of the resin compositions of Examples 1 to 4 was 90 to 94%. That is, the resin compositions of Examples 1 to 4 were sufficiently crosslinked at 150 ° C. and cured. Further, the conductive adhesives of Examples 1 to 4 have a large adhesive strength and a specific resistance of about (0.44 to 0.68) × 1.
It can be seen from Table 1 that it is as small as 0 ^-4 Ω · cm. Furthermore, the initial pencil hardness of the cured product of the conductive adhesive of Examples 1 to 4 was 6B.
Met. That is, the cured products of the conductive adhesives of Examples 1 to 4 were soft and excellent in flexibility. The pencil hardness hardly changed by heating at 150 ° C. for 1000 hours.
In other words, the cured products of the conductive adhesives of Examples 1 to 4 were excellent in heat resistance and hardly changed with time in hardness.

On the other hand, the cured product of the conductive adhesive of Comparative Example 1 using an acrylic polyol having 150 hydroxyl groups in one molecule as a hydroxyl-containing polymer compound has a pencil hardness of B High and 2H due to heating. That is, Comparative Example 1 was inferior in flexibility and heat resistance as compared with Examples 1 to 4. Further, the cured product of the conductive adhesive of Comparative Example 2 using a hydroxyl group-containing polymer having three hydroxyl groups in one molecule was inferior in heat resistance as in Comparative Example 1. Comparative Example 3 was similarly inferior in flexibility and heat resistance. In the case of Comparative Examples 4 and 5 using an epoxy compound containing no polyester unit or polyether unit in the molecular skeleton constituting the main chain, the resin composition and the conductive adhesive did not cure even when heated at 150 ° C. for 1 hour. It was sufficient, the adhesive strength of the conductive adhesive was low, the specific resistance was large, and the solvent-soluble component was large.

[0049]

As described above, the resin composition of the present invention has a high flexibility even when a large amount of filler such as a conductive filler is mixed, and the flexibility is long. To give a cured product that does not change over time. Also,
The conductive adhesive of the present invention is excellent in flexibility, heat resistance, conductivity and the like. Therefore, the conductive adhesive of the present invention is particularly suitable for bonding a vibrator component to an electrode or an electronic circuit, or for bonding a vibrator and a lead wire.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01B1 / 20 H01B 1/20 D // C08G 18/16 C08G 18/16 (72) Inventor Yukimasa Wakabayashi Washinomiya-cho, Kita-Katsushika-gun, Saitama 5-13-1, Sakurada Fujikura Chemical Co., Ltd.

Claims (5)

[Claims] 1. A resin composition comprising the following components (A) to (D). (A) an aliphatic compound having a molecular skeleton constituting a main chain and having a molecular weight of 1,000 or more containing a polyester unit or a polyether unit, and having a functional group containing carbon atoms of the polyester unit or the polyether unit; A hydroxyl group-containing polymer compound having 4 or more hydroxyl groups at both molecular ends, and (B) an aliphatic compound having a main chain comprising a polyester unit or a polyether unit, wherein the polyester unit or An epoxy compound having 4 or more carbon atoms in the polyether unit except for those included in the functional group, having an alicyclic epoxy group at both molecular terminals, and having an epoxy equivalent of 480 or more, (C) 1 A silane compound having at least one hydroxyl or alkoxy group bonded to a silicon atom in the molecule, (D) an aluminum chelate Compound,
At least one chelate compound selected from a titanium chelate compound and a zirconium chelate compound. 2. The hydroxyl-containing polymer compound (A) is 30 to 85% by weight based on the total amount of the hydroxyl-containing polymer compound (A) and the epoxy compound (B), and the epoxy compound (B) The resin composition according to claim 1, which is contained in a proportion of 70 to 15% by weight. 3. The composition according to claim 1, wherein the silane compound (C) is contained in a proportion of 15 parts by weight or less based on 100 parts by weight of the total of the hydroxyl group-containing polymer compound (A) and the epoxy compound (B). 2. The resin composition according to 1. 4. The block isocyanate compound is used in an amount of 2 to 25 parts by weight based on 100 parts by weight of the epoxy compound (B).
The resin composition according to any one of claims 1 to 3, which is added in a ratio of parts by weight. 5. The resin composition according to claim 1, which is 5 to 30% by weight and the conductive filler is 95 to 70% by weight.
A conductive adhesive comprising: