JPS62179583A - Adhesive composition - Google Patents

Abstract

PURPOSE:To obtain an adhesive composition which has excellent flexibility, heat resistance, electrical insulation properties, mechanical strength, etc., and is suitable for applications wherein properties such as flexibility and insulation properties are important, by incorporating a specified modified olefin rubber into a thermosetting resin prepolymer. CONSTITUTION:100pts.wt. ethylene-alpha-olefin rubber (e.g., an ethylene-propylene rubber) is subjected to addition reaction with 0.01-20pts.wt. monomer having an amino, hydroxyl, epoxy, carboxyl or acid anhydride group (e.g., maleic anhydride) to give a modified olefin rubber. 1-200pts.wt. this modified olefin rubber is mixed with 100pts.wt. prepolymer of a thermosetting resin (e.g., an epoxy resin or a phenolic resin) to give an objective adhesive composition. This adhesive composition is suitably used for bonding of a copper foil to a printed circuit board or bonding of elements to each other in the electronics field.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermosetting resin adhesive composition, and more specifically to an adhesive composition that requires not only flexibility but also heat resistance and electrical insulation properties. It is related to.

[Conventional technology]

Generally thermosetting resins, especially phenolic resins.

Epoxy resins have strong mechanical strength, excellent electrical properties as an insulator, and are also excellent in many respects such as heat resistance and chemical resistance.

However, since such resins lack flexibility, when used as adhesives, coating agents, etc., their peel strength and impact strength against metals, porcelain, various plastics, etc. are extremely low.

Various elastomers are available to improve this drawback.

In particular, studies have been made to improve impact resistance by imparting flexibility to the resin by using acrylonitrile-butadiene copolymer rubber, etc., which have excellent compatibility.

[Problem that the invention seeks to solve]

In recent years, rapid technological advances mainly in electronic devices have led to demands for even better thermosetting resin materials. Conventionally, as a result of modifying thermosetting resins with polar rubbers such as acrylonitrile-butadiene rubber, which have relatively good compatibility, although the impact resistance increased by several hundred, the electrical insulation properties usually deteriorated. Met.

On the other hand, with the recent development of the electrical and electronic industries, adhesives for printed circuit boards and the like have come to be required to have extremely strict electrical insulation properties.

[Means for solving problems]

As a result of intensive study on the above-mentioned technical problem, the present inventors discovered that olefin rubber, more specifically ethylene-α-
Thermosetting using a modified olefin rubber in which a monomer having an amino group, a hydroxyl group, an epoxy group, a carboxyl group, or an acid anhydride group is added to an olefin rubber from 0.01 to 20 parts per 100 parts of rubber. By modifying the resin, we have found that it is possible to obtain an adhesive composition that has excellent adhesive strength, mechanical strength, and impact resistance while keeping the insulation properties extremely low compared to conventional methods. The present invention has been achieved.

That is, in the present invention, a monomer having an amino group, a hydroxyl group, an epoxy group, a carboxyl group, or an acid anhydride group is added to the ethylene-α-olefin rubber based on 100 parts by weight of the thermosetting resin prepolymer per 100 parts by weight of the rubber.
．． Modified olefin rubber 1 added with 01 to 20 parts by weight
An adhesive composition is provided, characterized in that it contains 200 parts by weight.

The adhesive composition of the present invention refers to an adhesive composition or a coating composition.

Thermosetting resin prepolymers used in the present invention include phenol resins and epoxy resins.

Examples include melamine resin, unsaturated polyester resin, and prepolymer before alkyd resin conversion, but unsaturated polyester resin, phenol resin, epoxy resin prepolymer, and more preferably phenol resin from the viewpoint of adhesion to metals, resins, etc.

It is an epoxy resin prepolymer.

As the modified olefin rubber, two or more monoolefins or at least one monoolefin that can be further copolymerized with a Ziegler-Natsuta catalyst represented by a combination of a vanadium compound and an aluminum compound are used.
It can be obtained by using essentially amorphous olefin rubber obtained by copolymerizing various polyenes and adding reactive monomers having various functional groups thereto.

Examples of the amorphous olefin rubber include ethylene-α-olefin rubber (EPM) and/or ethylene-α-olefin-diene monomer rubber (EPDM). Here, the α-olefin is C1 to C1+ α-
Olefin.

Namely, propylene, butene-1, hexene-1, and octene-1 can be mentioned, but propylene is preferred.

Examples of reactive monomers added to olefin rubber include monomers containing an amino group, hydroxyl group, epoxy group, carboxyl group, or acid anhydride group.6 Specifically, monomers containing an amino group Examples of the compounds include diethylaminoethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, and vinylpyridine.

As a monomer containing a hydroxyl group.

Examples include hydroxypropyl (meth)acrylate and hydroxyethyl (meth)acrylate.

Examples of monomers containing epoxy groups include glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, and the like.

Monomers containing carboxyl groups or acid anhydride groups include acrylic acid, methacrylic acid, ethacrylic acid,
maleic acid, maleic anhydride, fumaric acid, itaconic acid,
Itaconic anhydride.

Examples include α, β-unsaturated carboxylic acids such as Himic acid and Himic acid anhydride, or acid anhydrides thereof.

Among these, monomeric compounds containing a carboxyl group or an acid anhydride group are preferred from the viewpoint of ease of carrying out the addition reaction operation to the olefin rubber, and among these, maleic anhydride is particularly preferred. Furthermore, maleic anhydride is widely used as a curing agent for thermosetting resins, mainly for epoxy resin applications.

It is more preferable since it does not adversely affect the thermosetting resin even if it remains as an unreacted monomer.

The amount of these modified monomers added to the olefin rubber is 0.01 to 20 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of rubber.

If the amount is less than 0.01 part by weight, the amount of functional groups introduced is small, resulting in poor reactivity with the thermosetting resin, and as a result, good adhesive strength cannot be obtained. If it exceeds 20 parts by weight, properties such as electrical properties and moisture resistance will deteriorate.

Regarding the addition reaction of monomers containing various functional groups to olefin rubber, the method described in Japanese Patent Publication No. 39-6384 can be used. That is, the olefin rubber and various monomers can be mixed and heated in a solid state to cause the reaction to occur. The heating method may be either a closed kneader or a continuous heating reaction using an extruder or the like. At this time, a portion of peroxide may be used to accelerate the reaction.

The blending ratio of the modified olefin rubber to the thermosetting resin prepolymer may vary depending on the purpose.
The amount is 1 to 200 parts by weight, preferably 10 to 100 parts by weight, per 0 parts by weight of the modified olefin rubber. If the modified olefin rubber is less than 1 part by weight, the effect of imparting flexibility to the thermosetting resin is poor, and when used as an adhesive, the peel strength and impact resistance are insufficient. If the amount exceeds 200 parts by weight, the inherent characteristics of thermosetting resins such as high strength, heat resistance, and solvent resistance will deteriorate.6 Olefin-based thermosetting resin prepolymer and various functional groups added There are no restrictions on the method of mixing the rubber, and a closed mixer such as a Banbury mixer, a roll, an extruder, etc. can be used depending on the rubber/resin mixing ratio.

Alternatively, a modified olefin rubber and a thermosetting resin prepolymer or a curing agent may be preliminarily reacted to form an adduct of the two.

Furthermore, in the case of a solution-type adhesive, a thermosetting resin prepolymer and a modified olefin rubber can be mixed together at the time of melting.

Moreover, in the case of an adhesive solution, both can be mixed at the time of dissolution.

Further, the rubber/resin mixed composition according to the present invention may contain anti-aging agents, stabilizers, plasticizers, softeners, various inorganic and organic fillers, reinforcing agents, and cross-linking agents as required.

The composition obtained according to the present invention is widely used as an adhesive mainly in the electrical and electronic fields, and since it has excellent heat resistance, it can also be widely applied to uses other than the above-mentioned fields.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these.

Example-1 Ethylene-propylene rubber (manufactured by Japan Synthetic Rubber Co., Ltd. JSR
EPII Mooney viscosity ML1. .

(100°C) = 40) 162 parts by weight of maleic anhydride and 0.6 parts by weight of cumene hydroperoxide per 100 parts by weight
Parts by weight were transferred into a closed Banbury mixer preheated to 120 to 140°C, and kneaded at 180°C for 5 minutes.

The obtained modified EP (A) was thoroughly kneaded at 150° C. in a closed mixer according to the recipe shown in Table 1 to prepare an adhesive composition.

The obtained adhesive composition was used to adhere rolled steel plates (thickness: 1.6 mm, washed and degreased with trichlene), and the adhesive strength was determined according to JIS K6850 by tensile shear bond strength (tensile speed: 5 m10 + in). ) and JIS
According to K6854, T-type peeling adhesive strength (tensile speed 50
We/win). The curing conditions for the adhesive were 150° C. for 30 minutes. The volume resistivity value is Yokomizo Hulett-Packard ■1116008A cell table-1 (
Epoxy resin adhesive composition formulation example-2 Under the same conditions as in Example-1, an epoxy resin adhesive composition was prepared by adding 10 parts of modified EP (A) to the epoxy resin prepolymer. The results are shown in Table 2.

Example 3 In Example 1, glycidyl methacrylate was used instead of maleic anhydride, and ethylene propylene rubber (E
P-11) to obtain modified EP (I3).

Using this, an epoxy resin adhesive composition was obtained in the same manner as in Example 1 and evaluated in the same manner, and the results are shown in Table 2.

Example-4 In Example-1, diethylaminoethyl methacrylate was used instead of maleic anhydride and kneaded with ethylene propylene rubber (EP-11) to obtain modified EP (C). Using this, an epoxy resin adhesive composition was obtained in the same manner as in Example 1 and evaluated in the same manner, and the results are shown in Table 2.

Comparative Examples-1, 2, 5 In Examples-1 and 2, J instead of modified EP (A)
An epoxy resin adhesive composition was obtained using SREP-11 as it was without modification. Note that Comparative Example 3 is an example in which no rubber was blended at all. The obtained adhesive composition was evaluated in the same manner as in Example-1, and the results are shown in Table-2.

Example 5 Using the modified EP (A) obtained in Example 1, a phenolic resin adhesive composition was prepared by kneading the modified EP (A) with a roll and then heating according to the recipe.

Formula of phenolic resin adhesive composition> 100 parts by weight of Kash modified phenolic resin prepolymer modified EP
(A) 5Q n Methyl Ethyl Ketone 350 Using the obtained adhesive composition, steel plate #304 was polished with No. 800 abrasive paper and degreased with methyl ethyl ketone, and vinyl chloride sheet (made by Logom@4) was degreased with methyl alcohol. seed)
This adhesion is determined according to JIS K685.
A 180 degree peel strength test was conducted in accordance with 4.

The measurement conditions were adhesive application 11 it 150-250g/open time 25°C 3 minutes tensile speed 200+wa/win.

In addition, a film was prepared on an aluminum plate using the above adhesive composition, and its volume resistivity (room temperature) was 6111.
Established.

The above measurement results are shown in Table-3.

Example-6 Ethylene-propylene rubber 1 was prepared in the same manner as in Example-1.
Modified EP (D) was prepared by adding 0.51 parts of maleic anhydride to 0.00 parts by weight, and an adhesive composition was prepared according to Example-5. Evaluation was carried out in the same manner as in Example-5, and the results are shown in Table-3.

Example 7 In Example 5, an adhesive composition was prepared using the modified EP (B) obtained in Example 3 instead of the modified EP (A). Evaluation was carried out in the same manner as in Example 5, and the results are shown in Table 3.

Comparative Example-4 In Example-5, Lini J S instead of modified EP (A)
Adhesive compositions were prepared using modified RE P-11. The same evaluation as in Example 5 was performed and the results are shown in Table 3.

Comparative Example-5 In Example-5, an adhesive composition was prepared using acrylonitrile-butadiene rubber, JSRN22O3 (manufactured by Japan Synthetic Rubber Co., Ltd., bound acrylonitrile 41%, Mooney viscosity 56), instead of modified EP (A). Example-
The same evaluation as in No. 5 was conducted, and the results are shown in Table 3.

Example-8 In Example-5, the total amount of modified EP (A) was 10 parts, and 10 parts of N22O8 was added to prepare an adhesive composition. The same evaluation as in Example 5 was carried out, and the results are shown in the table.
Shown in 3.

As is clear from Table 2, the adhesive composition of the present invention has sufficiently high tensile shear strength and peeling.

It was confirmed that it has excellent mechanical strength and flexibility. On the other hand, Comparative Example 1.2 using unmodified EP has insufficient shear strength and peel strength, and Comparative Example 3 has insufficient peel strength.

Furthermore, Table 3 shows that the adhesive composition of the present invention exhibits good peel strength. On the other hand, 1 Comparative example using normal EP-4
That is not enough.

Further, in Comparative Example 5 using acrylonitrile-butadiene rubber which has good compatibility with phenol resin, the adhesive force is good but the electrical resistance is low. (NBR) It can be said that the adhesive composition of the present invention has an excellent balance between the two.

Furthermore, as can be seen from Example 8, it is clear that a material with an excellent balance of adhesive strength and electrical resistance can be obtained by using modified EP and NBR in combination.6 [Effects of the Invention] From the results of Example As such, the thermosetting resin-based adhesive composition using the modified EP of the present invention can impart good flexibility while maintaining the excellent mechanical strength of the thermosetting resin. . Therefore, it can be used in adhesives that require flexibility, coating agents that also require crack resistance, and the like.

In particular, since it has good electrical resistance, it can be said to be particularly effective as an adhesive for electrical applications that require insulation, such as an adhesive for printed circuit boards.

Due to its properties, the adhesive composition according to the present invention can be used for adhesion between printed wiring boards and copper foil, and for adhesion between elements in the electronics field or for packaging.

It is also ideal for adhesive applications that require electrical insulation, such as bonding between speaker materials and bonding liquid crystals.

Furthermore, due to its good adhesive strength, it is effective for adhesion between metals and plastics such as vinyl chloride resin, for which conventional nitrile rubber or gloloprene rubber-modified thermosetting resin adhesives have been used. . In this case, since the modified olefin rubber contains almost no unsaturated bonds, it has better weather resistance and heat resistance than conventional rubber-modified adhesives.

Claims (3)

[Claims] (1) A monomer having an amino group, a hydroxyl group, an epoxy group, a carboxyl group, or an acid anhydride group is added to the ethylene-α-olefin rubber to 100 parts by weight of the thermosetting resin prepolymer. 0.01 per hit
Modified olefin rubber 1 to 200 added with 20 parts by weight
An adhesive composition characterized in that it contains parts by weight. (2) The adhesive composition according to claim 1, wherein the monomer is maleic anhydride. (3) The adhesive composition according to any one of claims 1 to 2, wherein the thermosetting resin is an epoxy resin or a phenol resin.