JPS63183977A - Adhesive composition having high insulation - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent electrical insulation, adhesivity and flexibility and useful as an adhesive, binder, etc., by compounding a dimer acid epoxy resin, a bismaleimide-triazine resin and an acrylonitrile- butadiene rubber at specific ratios. CONSTITUTION:The objective composition contains (A) 100pts.wt. of a dimer acid epoxy resin (e.g. a resin produced by epoxidizing carboxylic acid of a dimer acid with epichlorohydrin), (B) 50-150pts.wt., preferably 60-120pts.wt. of a bismaleimide-triazine resin and (C) 5-80pts.wt., preferably 20-50pts.wt. of an acrylonitrile-butadiene rubber (preferably having functional groups such as amino group, vinyl, group, epoxy group, etc.), as essential components. The component B is preferably composed of 5-90wt.% bismaleimide, 5-90% triazine and 5-90% reaction product of bismaleimide and cyanic acid ester.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a highly insulating adhesive composition, and is particularly intended for use in compositions such as adhesives, binders, coating materials, and other molding materials. The object of the present invention is to provide a composition useful as a.

(Prior art) Dimer acid-based epoxy resins have characteristics such as excellent adhesion and heat resistance, and are mainly used in the fields of laminated products and adhesives. Diene rubbers such as butadiene, NBR%SBR, etc. are often added to give flexibility.However, there is a problem that the addition of these rubbers reduces the heat resistance and insulation properties of the epoxy resin. There is a need for the development of highly insulating adhesives that have properties and flexibility.

(Structure of the Invention) As a result of intensive studies to solve the above-mentioned problems, the present invention consists of 100 parts by weight of dimer acid-based epoxy resin, 50 to 150 parts by weight of bismaleimide-triazine resin, and 5 to 80 parts by weight of acrylonitrile-butadiene rubber. The present invention has been completed based on the discovery that a highly insulating adhesive composition containing the above-mentioned part as an essential component can solve the above-mentioned problems.

The present invention will be explained in detail below.

The dimer acid-based epoxy resin used in the present invention is one in which the carboxyl group of dimer acid is epoxidized with epichlorohydrin, or one in which an epoxy resin is reacted with dimer acid, and these resins may be used alone or in combination of two or more. used.

Next, the bismaleimide-triazine resin contains 5 to 95% by weight of bismaleimide and 95 to 95% by weight of cyanate ester.
A mixture of 5% by weight is dissolved in a soluble solvent and reacted. Depending on the reaction temperature conditions, the resin content produced is 5 to 90% by weight of bismaleimide and 5 to 90% of triazine.
Weight %, bismaleimide-cyanate ester reaction product 5~
The content was adjusted to be within the range of 90% by weight. Also preferred are bismaleimide-triazine resins, including those modified by adding a urethane compound or an acrylic compound after or before the reaction, and these are used alone or in a mixture of two or more.

The acrylonitrile-butadiene rubber used in the present invention preferably has one or more functional groups selected from amine groups, vinyl groups, epoxy groups, and carboxyl groups, which may be used alone or in combination of two or more. and use it.

To obtain the insulating adhesive composition of the present invention, 100 parts by weight of the above-mentioned dimer acid type epoxy resin, 50 to 150 mIt parts of bismaleimide-triazine resin, preferably 60 to 1 mIt part
20 parts by weight, acrylonitrile-butadiene rubber 5-8
0 parts by weight, preferably 20 to 50 parts by weight, may be mixed into the car or heated and mixed.

The reason for specifying the mixing ratio in this case is that the bismaleimide
If the amount of the triazine resin is less than 50 parts by weight, satisfactory insulation properties cannot be imparted to the adhesive of the present invention, and if the amount is more than 150 parts by weight, flexibility will be lost. Further, if the amount of acrylonitrile-butadiene rubber is less than 5 parts by weight, flexibility and adhesion cannot be imparted satisfactorily, and if it is more than 80 parts by weight, insulation properties are lost.

In addition, what is necessary is just to heat at 40-80 degreeC for 1-30 hours at the time of mixing. In this case, an organic solvent can be used if necessary, and the solvent preferably has a relatively high solubility for the above three components, such as ethers such as 1,4-dioxane, ketones such as methyl ethyl ketone, Aromatic hydrocarbons such as toluene, N-methyl 2-pyrrolidone, etc. are used alone or in combination of two or more. Although the adhesive composition is applied in a solution state, it is preferable to use the above-mentioned organic solvent as the solvent and adjust the concentration to 10 to 70%. The insulating adhesive composition of the present invention is provided with flexibility and softness by the acrylonitrile-butadiene rubber component, adhesive properties by the dimer acid-based Ebixi resin component, and insulation and heat resistance by the bismaleimide-triazine resin. Because each component has its own characteristics, it has particularly excellent insulation properties. Because of these characteristics, the composition of the present invention is useful for applications such as adhesives for flexible printed wiring, binders for laminates, 8-stage adhesives, binders for molded products, or coating agents.

The present invention will be explained below with reference to Examples.

Example 1 20 parts by weight of Epicoat 871 (manufactured by Yuka Shell Epoxy Co., Ltd., dimer acid epoxy resin trade name), bismaleimide-triazine resin (diphenylmethane bismaleimide and 2,2-bis(4°-cyanurate phenyl)propane) 40 parts by weight of a 50 wt% solution of 50 wt% bismaleimide, 10 wt% triazine, and 40 wt% bismaleimide-cyanate ester reaction product dissolved in methyl ethyl ketone, HYCARCTBN
(B, F, manufactured by Goodrich Co., Ltd., modified acrylonitrile-butadiene rubber trade name) dissolved in methyl ethyl ketone, 9% solution, tooffiffi part, and 70 parts by weight of methyl ethyl ketone were weighed and added, and then 60 parts by weight of methyl ethyl ketone were added.
The composition of the present invention was obtained as a homogeneous solution by heating and mixing at .degree. C. for about 4 hours and then filtration. Using this composition as an adhesive, 50 μm Kapton (manufactured by Dupont, trade name of polyimide film) and 35 μm electrolytic copper foil were bonded together, resulting in a laminate with surface resistivity, peel strength, soldering heat resistance, The bending resistance was tested. The results are shown in Table 1.

In this case, the bonding method is as follows: First, the composition of the present invention is coated on a Kapton film that has been previously treated with low-temperature plasma so that the film thickness after drying is 20 μm.
The sample was pre-cured for 10 minutes, then roll-pressed with a 35 mm copper foil at 110°C using a hot roll, and then post-cured at 150°C for 5 hours.

Example 2 In Example 1, the bismaleimide-triazine resin was mixed with diphenylmethane bismaleimide and 2,2-bis(4゛
- Reaction product with cyanurate (phenyl) propane, 20 wt% bismaleimide, 20 wt% triazine
, bismaleimide-cyanate ester reactant 60wt%
An adhesive melt and a laminate of Kapton and copper foil were produced using the adhesive under the same conditions as in Example 1, except that the same adhesive was used. Next, various tests similar to those in Example 1 were conducted, and the results are shown in Table 1.

Example 3 In Example 1, the bismaleimide-triazine resin was a reaction product of diphenylmethane bismaleimide and KU-6575 (manufactured by Bayer AG, cyanate ester trade name), with 60 wt% bismaleimide and 30 wt% triazine.
W%, bismaleimide-cyanate ester reaction product 10
An adhesive solution and a laminate of Kapton and copper foil using the adhesive solution were produced under the same conditions as in Example 1, except that the adhesive solution was used at % wt%. Next, various tests similar to those in Example 1 were conducted, and the results are shown in Table 1.

Comparative Example 1 5 of the bismaleimide-triazine resin in Example 1
An adhesive solution and a laminate of Kapton and copper foil using the adhesive solution were produced under the same conditions as in Example 1, except that 40 parts by weight of the 0 wt% methyl ethyl ketone solution was replaced with 10 parts by weight. Next, various tests similar to those in Example 1 were conducted, and the results are shown in Table 1.

Comparative Example 2 An adhesive solution and Kapton using the same were prepared under the same conditions as in Example 1 using 8715 parts by weight of Epicoat, 70 parts by weight of HYCARC 7889% methyl ethyl ketone solution, and 40 parts by weight of the 50 wt% bismaleimide-triazine resin methyl ethyl ketone solution in Example 3. and a copper foil laminate. Next, various tests similar to those in Example 1 were conducted, and the results are shown in Table 1.

Comparative Example 3 In Example 1, HYCARCTBN(
B, F, Goodrich, modified acrylic, =
-IJ/l/-butadiene rubber trade name) 30wt%
An adhesive solution was prepared under the same conditions as in Example 1 except that 100 parts by weight of the methyl ethyl ketone solution was used, but it gelled during the preparation.

Example 4 Epicoat 87120rfL quantity part BT-2170 (bismaleimide, triazine resin trade name manufactured by Mitsubishi Gas Chemical Co., Ltd.)
50% solution of dissolved in methyl ethyl ketone, 10 parts by weight, 50% solution of BT-2164 (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name of urethane-modified bismaleimide triazine resin) dissolved in methyl ethyl ketone, 10!1 parts of BT
-A135 to -A (manufactured by Mitsubishi Gas Chemical Co., Ltd., acrylic modified bismaleimide triazine resin 60% solution) 10 parts by weight 1 (YCARATBN (B, F, Goodrich)
(Product name of modified acrylonitrile-butadiene rubber manufactured by Co., Ltd.)
Weighed 100 parts by weight of a 6% solution of 20% dissolved in methyl ethyl ketone and 70 parts by weight of methyl ethyl ketone, respectively.
After the addition, the composition of the present invention was heated and mixed at 60° C. for about 4 hours, and then filtered to obtain the composition of the present invention as a homogeneous solution.

Using this composition as an adhesive, 50 μm of Kapton and 35 μm of adhesive were used.
The surface resistivity, peeling strength, soldering heat resistance, and bending resistance of the resulting laminate were tested for surface resistivity, peel strength, soldering heat resistance, and bending resistance. The results are shown in Table 2.

In this case, the bonding method is to use Kapton film that has been previously treated with low-temperature plasma so that the film thickness after drying is 20 μm.
The above adhesive composition was applied so that the temperature was 1.
Pre-cure for 0 minutes, then use a heat roll to cure for 35 minutes.
After roll pressing with a μm copper foil at 10°C, post-curing was performed at 150°C for 5 hours.

Example 5 In Example 4, a 6 wt% methyl ethyl ketone solution of HYCARATBN xoo! HYCARA instead of i quantity part
50 parts by weight of 6t% toluene solution of TBN and HYc8R
Example 4 except that a mixture of 50 parts by weight of a 6 wt % toluene solution of HeTBN (B, F, manufactured by Goodrich, trade name of modified acrylonitrile-butadiene rubber) was used.
An adhesive and a laminate of Kapton and copper foil were made using the adhesive under the same conditions as described above. Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

Example 6 In Example 4, Epikot 871 was replaced with Epoto)
Using -YD-'172 (manufactured by Tobu Kasei Co., Ltd., trade name of dimer acid-based epoxy resin), the adhesive was dissolved and used under the same conditions as in Example 4, except that -AIO parts by weight were removed from BT-A135. Various tests similar to those in Example 4, in which a laminate of Kapton and copper foil was prepared, were conducted, and the results are shown in Table 2.

Comparative Example 4 An adhesive solution and a laminate of Kapton and copper foil using the same were prepared under the same conditions as in Example 4 except that BT2170, BT-2164 and BT-A 135 k-A were removed. Created. Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

Comparative Example 5 An adhesive solution and a laminate of Kapton and copper foil using the adhesive solution were produced under the same conditions as in Example 4 except that HKYCARATBN was omitted. Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

Comparative Example 6 An adhesive was melted and a laminate of Kapton and copper foil was produced using the adhesive under the same conditions as in Example 4, except that Epicoat 871 was omitted. Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

Comparative Example 7 In Example 4, 100 parts by weight of Epicoat 87120 was added to
An adhesive was melted under the same conditions as in Example 4, except that the parts by weight were increased, and a laminate of Kapton, copper, etc. was produced using the adhesive. Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

Comparative Example 8 In place of 100 parts by weight of a 6% methyl ketone solution of IYCARATBN in Example 4) IYCARCT[l
30% methyl ethyl ketone solution of N for 7 nights! An adhesive solution and a laminate of Kapton and copper foil using the adhesive solution were produced under the same conditions as in Example 4 except that the oomfL part was used.

Next, various tests similar to those in Example 4 were conducted, and the results are shown in Table 2.

(Efficiency of the invention) As explained above, the insulating adhesive composition of the present invention has excellent electrical insulation, adhesiveness, and flexibility. Suitable as adhesive for parts.

Claims (1)

[Scope of Claims] 1. A highly insulating adhesive composition containing as essential components 100 parts by weight of a dimer acid-based epoxy resin, 50 to 150 parts by weight of a bismaleimide-triazine resin, and 5 to 80 parts by weight of acrylonitrile-butadiene rubber. 2. The bismaleimide-triazine resin is composed of 5 to 90% by weight of bismaleimide, 5 to 90% by weight of triazine, and 5 to 90% by weight of the bismaleimide-cyanate ester reaction product. Highly insulating adhesive composition according to item 1.