JPS6340453B2 - - Google Patents

Description

[Detailed description of the invention]

Object of the Invention (Field of Industrial Application) The present invention relates to an adhesive composition for adhering another object to an adherend made of a non-polar polymeric material such as polypropylene or polyethylene. (Conventional technology) Polypropylene PP, polyethylene PE, ethylene-propylene non-conjugated diene terpolymer
EPDM, ethylene-propylene copolymer compound EPR
Synthetic resin molded products made of non-polar polymer materials such as 100% polyester, etc. have been used for various purposes in recent years. However, this non-polar polymer material contains acrylonitrile-butadiene-styrene terpolymer in the molecule.
Because it does not have the polar groups that ABS, nitrile butadiene rubber NBR, etc. have, it is extremely difficult to adhere to other objects, and the adhesive strength is not high. (Problems to be Solved by the Invention) Therefore, when attaching another object to an adherend made of a non-polar polymer material such as PP, PE, EPDM, EPR, etc., this invention lacks adhesive strength and the other object This aims to solve the problem that the adhesive peels off more easily than the adherend. Structure of the Invention (Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention provides that 50 to 800 parts by weight of an acrylic ester or a methacrylic ester, or a derivative thereof, is added to 100 parts by weight of rubber. 5 to 100 parts by weight of chlorinated polypropylene, and 50 to 400 parts by weight of a urethane compound having terminal isocyanate groups. (Function) The above means increases the adhesive force between the adherend made of a non-polar polymeric material and another object. (Example) Next, an example embodying the present invention will be described with reference to FIG. This adhesive 1 contains 1100 parts of natural rubber NR as a rubber, 1100 parts of methyl methacrylate as an acrylic ester or methacrylic ester or a derivative thereof, and benzoyl peroxide (hereinafter referred to as BPO) as a peroxide catalyst. 0.01
and chlorinated polypropylene (hereinafter referred to as cl-PP).
550 parts, 24,750 parts of toluene as an organic solvent, and 4, as a polyisocyanate for synthesizing a urethane compound having terminal isocyanate groups.
It consists of 750 parts of 4'-diphenylmethane diisocyanate, 2000 parts of polyethylene adipate as a polyol, 12,375 parts of toluene, and 12,375 parts of methyl ethyl ketone MEK. Here, the above-mentioned rubber, acrylic ester,
For each of cl-PP and urethane compounds, examples that can be used instead or supplementary explanations are provided. In addition to natural rubber NR, the above-mentioned rubbers include butadiene rubber BR, isobutylene-isoprene rubber.
Examples include IIR, isoprene rubber IR, nitrile butadiene rubber NBR, and styrene butadiene rubber SBR. In addition to methyl methacrylate, examples of the acrylic ester, methacrylic ester, or derivatives thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, Examples include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, and dodecyl acrylate. In addition, the blending ratio should be 50 to 800 parts per 100 parts of rubber. If it is less than 50 parts, the compatibility with the urethane compound will decrease and the adhesive strength will decrease, and if it is more than 800 parts, it will become hard and the adhesive will not work. This is because the agent layer becomes brittle. The mixing ratio of the above cl-PP is 5 parts per 100 parts of rubber.
The reason for setting the amount to 100 parts is because if it is less than 5 parts, the adhesive strength will decrease, and if it is more than 100 parts, the heat resistance will decrease and no improvement in the adhesive will be seen. As the polyisocyanate, in addition to 4,4'-diphenylmethane diisocyanate, 1,5-
Diisocyanates such as naphthalene diisocyanate, tolylene diisocyanate, 1,6-hexamethylene diisocyanate and derivatives thereof,
For example, as a derivative of 4,4'-diphenylmethane diisocyanate, An example is a mixture of Other examples include polyfunctional isocyanates such as 4,4,4'-triphenyltriisocyanate, 4,4'-dimethylmethane, and 2,2',5,5'-tetraisocyanate. In addition to polyethylene adipate, the polyols include polypropylene glycol (PPG).
Examples include ether polyols such as polyethylene glycol and polytetraethylene glycol, and ester polyols such as polybutylene adipate, polyethylene butylene adipate, and polypropylene adipate. The reason why the blending ratio of the urethane compound was set at 50 to 400 parts per 100 parts of rubber is because if it is less than 50 parts, the adhesive strength will decrease, and if more than 400 parts are added, no improvement in adhesive strength will be seen. be. Further, as a method for polymerizing the urethane compound in this example, the polyol and the polyisocyanate were reacted for 3 hours in dry nitrogen gas at 80°C to synthesize the urethane compound. In addition, ethylene glycol, propylene glycol, 1,4-
Butadiol, 1,5-pentanediol, 1,
A low molecular polyol such as 6-hexanediol may be added, or a low molecular diol may be added as a chain extender. Next, in order to confirm the effect of the adhesive force of the adhesive 1 of this example, specific examples 1 to 5 were used in which the adhesive 1 was mixed and used in the weight percentages shown in Tables 1a and 1b below.
The following tests were conducted on Specific Examples 6 to 9 in which the adhesive 1 was mixed and used in the weight parts shown in Tables 2a and 2b. That is, as shown in FIG. 1, a test piece 5 was prepared by adhering a bright molding 3 to the surface of a side protection molding (hereinafter referred to as side molding) 4 of an automobile via the adhesive 1 and double-sided adhesive tape 2. , a peeling test was conducted. The side molding 4 is made of a non-polar polymer material having the following weight parts, and is heated at 200°C.
It is injection molded in the molten state. Polypropylene (PP) 77 parts Polyethylene (PE) 15 parts Ethylene propylene rubber (EPR) 18 parts

【table】

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【table】

[Table] In the above bonding method, Adhesive 1 was applied to the surface of the side molding 4 by brushing and air-dried for 20 minutes at room temperature. Thereafter, a double-sided adhesive tape 2 having an acrylic adhesive 2a on both sides and an acrylic sponge 2b inside is applied to the adhesive side of the bright molding 3, and also applied to the dry surface of the adhesive 1. . Further, as a method for applying the adhesive 1, any method other than the above-mentioned brushing, dip coating, spray coating, etc. may be used. As the sponge 2b of the double-sided adhesive tape 2, in addition to the acrylic material, polyethylene, chloroprene, etc. can be used. Further, the acrylic adhesive 2a is made of butylene acrylate, butyl methacrylate, 2
- Composed of ethylhexyacrylate, etc. The peeling test was carried out 24 hours after the Bright Molding 3 was pasted. Specifically, a 180° peeling test was conducted by chucking the bright molding 3 and the side molding 4 at a tensile speed of 200 mm/min. Furthermore, as specific example 10, 183 parts of natural rubber,
183 parts of methyl methacrylate, 92 parts of cl-PP and 4,
750 parts of 4-diphenylmethane diisocyanate,
2000 parts of polyethylene adipate and solid content 1:5
mixed in the ratio of Furthermore, for comparative study, as shown in Table 3, similar tests were conducted for Comparative Examples 1 to 5 in which a rubber adhesive was used in place of Adhesive 1. The results are shown in Table 4 as the foam destruction rate of the double-sided adhesive tape 2 (the ratio of the area of the sponge portion 2b of the double-sided adhesive tape destroyed and attached to the side molding 4 to the total area).

[Table] The adhesive used in Comparative Examples 1 to 3 was manufactured by Konishi Co., Ltd.
The adhesive used in Comparative Examples 4 and 5 is a product name manufactured by Cemedine Co., Ltd.

【table】

[Table] The foam destruction rate of the double-sided adhesive tape 2 was 0% in the conventional example and the comparative example, indicating that the sponge 2b part was not destroyed and was peeled off as is, whereas the specific example of this example was 75%. The above is shown. This indicates that the adhesive 1 used in this example has higher adhesion to the side molding 4 than the double-sided adhesive tape 2 alone or existing adhesives. Therefore, the adhesive 1 of the present invention can have strong adhesion to non-polar polymeric materials, which do not have excellent adhesion than conventional adhesives. Note that the present invention is not limited to the above-mentioned embodiments, and can be embodied as follows, for example. (1) In this example, one application and method is as follows:
Apply the adhesive 1 to the PP side molding 4,
Furthermore, the bright molding 3 is attached via the double-sided adhesive tape 2.
However, the application and method are not limited to this. For example, adhesive 1 may be applied to a PP car bumper and another object may be directly adhered to it, or it may be applied to a PE molding. It can also be applied and adhered to other objects. (2) In order to speed up the drying of the adhesive 1, a temperature of 100° C. or lower may be applied. If the temperature exceeds 100°C, the adhesive 1 and the polymer material may deteriorate. (3) In order to speed up the adhesive curing of the adhesive 1, catalysts such as triethylamine, triethyleneamine, and dibutyltin dilaurate, which are generally used in the urethane industry, can be used. (4) Adhesive 1 of this example shows particularly improved adhesion when non-polar materials are used, but it is not limited to this and can also be used with other polar materials, metals, etc. It can also be used as a primer. Effects of the Invention As detailed above, the adhesive of the present invention can provide strong adhesive strength to non-polar materials that conventionally have poor adhesive properties.

[Brief explanation of drawings]

The figure is a sectional view showing a test piece used in a peeling test conducted to confirm the effectiveness of the adhesive of the present invention. Adhesive...1.

Claims (1)

[Scope of Claims] 1. Mixed polymerization of 50 to 800 parts by weight of acrylic ester or methacrylic ester or derivatives thereof to 100 parts by weight of rubber, 5 to 100 parts by weight of chlorinated polypropylene, and a terminal polymer. An adhesive composition comprising 50 to 400 parts by weight of a urethane compound having an isocyanate group. 2. The adhesive composition according to claim 1, wherein the rubber and the acrylic ester or methacrylic ester or their derivatives are mixed and polymerized in the presence of a peroxide catalyst. 3. Claim 2, wherein the peroxide catalyst is benzoyl peroxide.
The adhesive composition described in . 4. The adhesive composition according to claim 1, wherein the urethane compound having a terminal isocyanate group comprises a polyol and a polyisocyanate.