JPS61174238A - Bondable composition - Google Patents

Abstract

PURPOSE:To improve the adhesion of paints or adhesives to the surfaces of vulcanized polyolefin rubbers, by coating said surfaces with a compsn. consisting of a hydrocarbon polymer and an alkyl hypohalite. CONSTITUTION:Examples of the above hydrocarbon polymers are polyhydroxypolyolefins which have an average MW of 1,000-5,000 and contains at least one hydroxyl group at its terminal and whose main chain is satd. or partially satd. Examples of the alkyl groups of the alkyl hypohalite are normal, secondary and tertiary alkyl groups, among which tertiary alkyl groups (e.g. tert-butyl) are preferred, because they are stable. As halogen, chlorine and bromine are preferred. The alkyl hypohalite is used in a quantity of pref. 0.01-300pts.wt. per 100pts.wt. polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Industrial Field of Application) The present invention relates to an adhesive composition that enhances the adhesion of paints, adhesives, etc. on textiles.

(Prior art) Polyolefin-based vulcanized rubbers, such as ethylene-propylene-diene ternary copolymer rubber (EPDM) and ethylene-propylene copolymer rubber (EPM), are similar to natural rubber (NR) and styrene-butadiene copolymer rubber (SBR). ), polybutadiene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), polychloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), and polyisoprene rubber (IR). Weatherability,
It is a rubber that has excellent properties such as excellent aging resistance and ozone resistance, and can be used in a wide range of temperatures from 150°C to 150°C, so it is currently used in many fields. came into use.

(Problem to be solved by the invention) However, since vulcanized rubbers such as EPDM, F, and PM do not contain polar groups in their main chains, the resulting coating film is easy to peel off even when paint is applied. Therefore, it is currently extremely difficult to coat this vulcanized rubber.

A number of countermeasures have already been attempted to address these shortcomings.

For example, (1) polish the surface with a wire brush, sandpaper, etc. (2) Perform ultraviolet irradiation. (3) Immerse in concentrated sulfuric acid. (4) Treatment with a mixed solution of organic monocarboxylic acid and phosphoric acid. (5) Treat with aldehydes.

(6) Between chlorinated polypropylene and ethylenediamine
Apply the mixture. (7) Treatment with isocytenate iodide. (8) Oxidize the surface by exposing it to ozone. (9)
Examples of such methods include treatment with an epoxy resin modified with a polymerized fatty acid, an amine curing agent, and an organic solvent.

However, in these conventional processing methods, (1) unevenness in the polishing state tends to occur. ■There are hygiene problems due to the generation of dust. ■Causes deterioration of vulcanizate.

■Handling processing agents is dangerous. ■The processing process is complicated. ■Requires special processing agent. ■In addition to drawbacks such as the high cost of equipment, even with such treatments, it could not always be said that the adhesion of paints and adhesives was sufficient.

In order to solve the above problems, the present inventors developed a primer composition made of a hydrocarbon polymer containing hydroxyl groups in the molecule. (Japanese Unexamined Patent Publication No. 50-14-2695) As a result of repeated research on the adhesion of this primer composition, it was found that - We have discovered an adhesive composition that has sufficient adhesion to vulcanized rubber, and have completed the present invention.

Structure of the Invention (Means for Solving Problems) The present invention provides a primer having at least 1 (lllI) hydroxyl group at the end to strengthen the adhesion of paints, adhesives, etc. applied to the surface of polyolefin vulcanized rubber. An adhesive composition was composed of a hydrocarbon polymer whose main chain was saturated or partially saturated and an alkyl hypohalide.

(Function) Since polyolefin vulcanized rubber does not contain polar groups in its molecules, it is difficult for paints, adhesives, etc. to adhere to it in a double-layered manner.

Therefore, if a composition consisting of a hydrocarbon polymer containing a hydroxyl group in the molecule and an alkyl hypohalide is applied to the surface of the same rubber, the surface will be activated by halogen and will be resistant to various paints, adhesives, etc. Provides excellent adhesion. (Example) Hereinafter, the adhesive composition of the wood invention will be explained by giving specific examples.

The hydrocarbon polymer having a hydroxyl group in the molecule used in the present invention preferably has one or more hydroxyl groups in one molecule.
Weight: Average molecular weight 500-5 with 1.8-5.0 hydroxyl groups and saturated or partially saturated main chain
10,000, preferably 1,000 to 20,000 polyhydroxybolybutadiene polymer (Japanese Patent Application Laid-Open No. 50-142695).

And the average molecule with a hydroxyl group at the child end is N1000~
5000 polyhydroxypolyolefin (manufactured by Mitsubishi Chemical Industries, trademark 2 [Polytail HJ, [Polytail HAJ]
) can be exemplified.

The feature of the wood invention is that an adhesive composition is prepared by blending an alkyl hypohalide with the above hydrocarbon polymer, and the alkyl group of this alkyl hypohalide may be a normal, secondary or tertiary alkyl group. Among these, stable tertiary alkyl groups such as tertiary butyl and tertiary amyl are preferred.

Alternatively, it is also possible to use halogenated alkyl groups such as dichloromethyl, trichloromethyl or fluoromethyl.

Moreover, it is preferable to use either chlorine or bromine as the halogen.

Although there are some unknown points about the reaction mechanism between the above hydrocarbon polymer and alkyl hypohalide, the hydrocarbon polymer is activated by the halogen in the alkyl hypohalide, resulting in strong adhesion to various paints, adhesives, etc. It is thought that power is given.

Further, the blending ratio of the hydrocarbon polymer and the alkyl hypohalide is preferably 0.01 to 300 parts by weight of the alkyl hypohalide per 100 parts by weight of the polymer.
More preferably, it is 0.01 to 1.0 parts by weight.

In order to apply this adhesive composition to polyolefin vulcanized rubber, it may be diluted with a solvent to lower the viscosity before use.

Solvents used at this time include saturated hydrocarbons such as n-hexano and cyclohexane, aromatic hydrocarbons such as Hensen, toluene and xylene, chlorinated hydrocarbons such as chloroform, carbon tetrachloride and trichlorethylene, or acetic acid esters. They are ketones.

When used diluted with these solvents, the concentration of the adhesive composition is preferably 30% or less, and if it is 30% or more, solid content may precipitate at room temperature.

Further, the composition does not require any special equipment and can be easily applied by ordinary coating methods such as dipping, brushing, and spraying.

Furthermore, since the same composition is a one-component type, it has a very long pot life.
If the viscosity increases by -1 due to evaporation of the solvent, the viscosity may be adjusted by adding the solvent again.

Next, the polyolefin vulcanized rubber to which the composition is applied contains EPDM, EPM, etc., as well as other rubber components such as NRXS in an amount within a range that does not lose these properties.
Those containing BR, BR, IIR, CR, NBR, IR and other resin components such as polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), etc. are also included.

The content of these rubber components is usually less than twice the amount of EPDM or EPM.

In addition, the rubber components to be applied include commonly used compounds, such as sulfur, morpholine disulfide, dicumyl peroxide, etc. as vulcanizing agents, and 2-mercaptohendithiazole and dimethyldithiocarbamic acid as vulcanization accelerators. Zinc, tetramethylthiuram disulfide, etc. ■ Phenyl-α-naphthylamine, 2,6-sheet t- as an anti-aging agent, antioxidant, and ozone deterioration inhibitor.
Butyl-p-cresol, etc.; Carbon, hydrated silicic acid, magnesium carbonate, clay, etc. as fillers; Possible W
Dioctylsehake-1, mineral oil, etc. are added as agents.

Next, the effects of the present invention will be specifically explained using the following examples.

Examples 1 to 4 are self-explanatory? After applying the adhesive composition of the present invention to various rubber products for J+ cars, urethane paint or acrylic adhesive was applied.

Example 1: The polyolefin vulcanized rubber for grass run used in the sliding parts of the grass land assash with the wind glass has the composition shown in Table 1, as an example.

(Hereinafter, all parts are parts by weight.) After extrusion molding an EPDM compound having the composition shown in Table 1, 1
It was vulcanized at 60°C for 30 minutes to produce a glass run base material for automobiles.

An adhesive composition having the composition shown in Table 2 was applied to the surface of this glass run base material, and after air drying for 1 hour, a urethane paint having the composition shown in Table 3 was applied and cured at room temperature for 24 hours.

In addition, the urethane prepolymer in Table 3 is a mixture of 40 parts of urethane prepolymer (B) to 100 parts of urethane prepolymer (A) shown below, and the solvent is toluene, cyclohexanone, trichloride, etc. "It is a mixed solvent of ethylene and tetrachlorethylene.

Urethane prepolymer (A): The composition shown in Table 4 was reacted in dry nitrogen gas at 80°C for 3 hours to obtain a urethane prepolymer.

Urethane prepolymer (B): Further, the composition shown in Table 5 was reacted at 80° C. for 3 hours in dry nitrogen gas to obtain a urethane prepolymer.

Example 2, Door Weatherstrip A weatherstrip base material for sealing the gap between the body and the door of an automobile has, as an example, a composition shown in Table 6.

After extrusion molding an EPDM composition having the composition shown in Table 6 above, it was vulcanized at 200°C for 5 minutes to produce a weatherstrip base material.

An adhesive composition having the composition shown in Table 2 above was applied to the surface of this weatherstrip base material, and after air drying for 1 hour, a urethane paint having the composition shown in Table 7 was applied, and after air drying for 1 hour at room temperature, Silicone oil (100,000 cSt, toluene 5%
solution) was applied.

Example 3: Electrostatic flocking product Some glass run products have electrostatic flocking processing using short fibers applied to the sliding portion of the glass.

The adhesive composition having the composition shown in Table 2 was applied to the surface of the glass run profiteer of Example 1, and after air-drying for 1 hour, a urethane adhesive having the composition shown in Table 8 was applied.

A urethane adhesive was prepared by reacting the formulations shown in Table 8 above at 80° C. for 3 hours in dry nitrogen gas.

Next, a pile made of nylon 66 short fibers was electrostatically flocked, and the adhesive was cured with hot air to obtain an electrostatic flocked product.

Abrasion resistance tests were conducted on the rubber products of Examples 1 to 3 above using the following method, and the results shown in Table 9 were obtained.

Testing machine: KI type abrasion tester Test conditions: Friction element glass (thickness 5II11) Load: 3 kg Friction element cycle: 60 times/min Friction element stroke: 145 m+i Test method: Attach the test piece to the above testing machine &J, as described above. The surface of the base moon is rubbed under the following conditions.

Good (no exposure of base material) Each of the products in Comparative Examples 1 to 3 below has been conventionally used as a primer for rubber products and the like.

Comparative Example - 1゜Hesokosol, J-534-1 (Trademark manufactured by Futari Ki Ink Chemical Industry Co., Ltd., linseed oil modified long oil alkyd resin) was dissolved in mineral haze, and cobalt naphthenate was added as a desiccant. was applied to the vulcanized rubber having the composition shown in Table 1, and after drying at room temperature for 24 hours, the urethane paint shown in Table 3 was applied.

Comparative Example 2 A solution of Orestar M2S-80AJ (trademark: Mitsui Toatsu, moisture-curing polyurethane resin) dissolved in toluene was applied to vulcanized rubber having the composition shown in Table 1, and the mixture was heated at room temperature for 24 hours.
After drying for a period of time, the urethane paint shown in Table 3 was applied.

Comparative Example-3゜"Ester Resin-20" (Trademark: Toyobo Co., Ltd., Kaibaowa Polyester) Methyl ethyl: Toluene-1
The solution dissolved in a mixed solvent of 9 was applied to the vulcanized rubber having the composition shown in Table 1, and after drying at room temperature for 24 hours, the urethane paint shown in Table 3 was applied.

The vulcanized rubber treated in Comparative Examples-1 to 3 above was subjected to the same wear resistance test as in Examples-1 to 3, and Table 10
I got the result.

×...Poor (exposure of base material) Next, a "burlap test" was conducted on the adhesion of the coating films of Examples-1 to 3 and Comparative Examples-1 to 3, and Table 11
I got the result.

Further, a 180° bending test was conducted to check the conformability of the coating films of the vulcanized rubbers treated in Examples 1 to 3, and they showed extremely good conformability.

Example 4, Resin molding: The molding that is attached to the side surface of the automobile body is attached to the body via, for example, a double-sided adhesive tape whose base material is polyethylene (PE) foam.

An adhesive composition having the composition shown in Table 2 was applied to the surface of this PE foam base material, and after air-drying for 1 hour, a commercially available acrylic adhesive used in the above-mentioned double-sided adhesive tape was applied thereon. This was attached to an acrylic-coated iron plate and left for 24 hours, and then the tensile shear strength was measured.

Shear strength... 1320 g/c Also, as a comparative example, a commercially available double-sided adhesive tape (Nitto Denko: 'No, 500>
was attached to an acrylic-coated iron plate and left for 24 hours, and then the tensile shear strength was measured.

Shear strength: 230 g/cd From the various test results detailed above, the adhesive strength of this adhesive composition was sufficient for use in various rubber products for automobiles.

Effects of the Invention As is clear from the test results of the above examples, the polyolefin vulcanized rubber coated with the adhesive composition of the present invention has extremely strong adhesion to paints and adhesives applied thereon. Granted.

Therefore, this adhesive fill composition is an excellent invention that can be used in a wide range of applications, not only for automobile rubber products of the acidic examples, but also as a primer for polyolefin vulcanized rubber that requires strong adhesion. It is.

Patent applicant: Toyoda Gosei Co., Ltd. Agent Patent attorney On 1) Hironobu 'snn-

Claims (1)

[Claims] 1. An adhesive composition comprising a hydrocarbon polymer whose main chain is saturated or partially saturated and has at least one hydroxyl group at the end, and an alkyl hypohalide.