JPH0380815B2 - - Google Patents

Description

[Detailed description of the invention]

Purpose of the Invention (Field of Industrial Application) The present invention aims to strengthen the adhesion of paints, adhesives, etc. applied to the surface of base materials made of polyolefin polymers (polyolefin vulcanized rubber, polyolefin synthetic resins), etc. The present invention relates to adhesive compositions for use in adhesive compositions. (Prior technology) There are many types of industrial rubber products and synthetic resin products, but especially polyolefin-based products such as ethylene-propylene-diene copolymer rubber (EPDM) and ethylene-propylene copolymer rubber (EPM). Vulcanized rubber or polypropylene (PP)
Polyolefin-based synthetic resins such as polyethylene (PE), natural rubber (NR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), and polychloroprene rubber (CR) ), various synthetic rubbers such as acrylonitrile-butadiene copolymer rubber (NBR), polyisoprene rubber (IR), or ABS resin, polystyrene resin (PS), vinyl chloride resin (PVC), acrylonitrile-styrene copolymer resin (AS) Compared to various synthetic resins such as ethylene-vinyl acetate copolymer resin (EVA), it exhibits excellent physical properties such as weather resistance, aging resistance, and ozone resistance, and can be used over a wide range of temperatures. Because it is a polymer with excellent features such as, it is used in many industrial fields. (Problem to be solved by the invention) However, since none of the above polyolefin vulcanized rubbers such as EPDM and EPM and polyolefin synthetic resins such as PP and PE contain polar groups in the main chain of their molecules, However, even if a paint or adhesive is applied to the surface of a base material made from these polymers, the resulting coating film has the disadvantage of being easy to peel off. Therefore, it is currently extremely difficult to coat the surface of a substrate made of these polymers, or to adhere these polymers to each other or to metals, synthetic resins, and the like. Although various countermeasures have been attempted in the past to address these drawbacks, there is a problem in that a satisfactory solution has not yet been found. In order to solve the above-mentioned problems, the present inventors have conducted repeated research on adhesive compositions that have strong adhesion to the surface of substrates made of polyolefin-based polymers. The present invention was achieved by discovering a composition that has strong adhesion to various synthetic resins and synthetic rubbers. Structure of the Invention (Means for Solving Problems) That is, the present invention comprises (1) at least one unvulcanized rubber composition selected from the following (2)
By employing an adhesive composition whose main components are a hydrocarbon polymer containing at least one functional group selected from the following () at the molecular end, or a derivative thereof, and (3) a halogenating agent, the above-mentioned It was an attempt to solve the problem. () Natural rubber, ethylene-propylene-diene copolymer rubber, ethylene-propylene-copolymer rubber, styrene-butadiene rubber, polybutadiene rubber, isobutylene-isoprene copolymer rubber, polychloroprene rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene Unvulcanized rubber of rubber () Hydroxyl group, allyl hydroxyl group, carboxyl group (function) A hydrocarbon polymer containing at least one functional group selected from the above () at the molecular terminal in the adhesive composition, or The derivatives exhibit good adhesive properties because they contain a functional group at the end of the molecule, and are also characterized by the ability to obtain compositions with various physical properties by reacting with various crosslinking agents. Further, by preparing a composition in which a halogenating agent is added to at least one unvulcanized rubber selected from () above, unvulcanized rubber molecules in the composition are crosslinked with each other by halogen, An adhesive composition having strong adhesion to various polymers can be obtained. Therefore, an adhesive composition is prepared by adding an unvulcanized rubber composition and a halogenating agent to the above hydrocarbon polymer or its derivative, and this is applied as an undercoat to the surface of a polyolefin polymer base material, Then, by applying various paints and adhesives thereon, these paints and adhesives are firmly adhered to the surface of the base material. (Example) Hereinafter, each component constituting the adhesive composition of the present invention will be explained in detail. (1) Unvulcanized rubber composition Unvulcanized rubber composition specifically includes unvulcanized natural rubber, EPDM, EPM, SBR, BR, IIR,
The main component is unvulcanized synthetic rubber such as CR, NBR, IR, etc., and it is a viscous composition obtained by dissolving these unvulcanized rubbers in a solvent. (2) Hydrocarbon polymers or derivatives thereof containing functional groups at the molecular ends. A hydrocarbon polymer containing a functional group at the end of the molecule is a hydrocarbon polymer that contains at least one hydroxyl group at the end of the molecule and whose main chain is saturated or partially saturated. (b) A polybutadiene polymer containing an allyl-type hydroxyl group at the end of the molecule. (c) It is a hydrocarbon polymer that contains a carboxyl group at the molecular end and has a saturated or partially saturated main chain. Furthermore, the above (a) hydrocarbon polymer containing at least one hydroxyl group at the end of the molecule and having a saturated or partially saturated main chain specifically refers to one or more hydroxyl groups in one monomer molecule, preferably Contains 1.8 to 5.0 hydroxyl groups and has a saturated or partially saturated main chain with an average molecular weight of 500
~50,000, preferably 1,000 to 20,000 polyhydroxypolybutadiene polymers
142695), or polyhydroxypolyolefin with an average molecular weight of 1,000 to 5,000 (manufactured by Mitsubishi Chemical Industries, Ltd., trade names "Polytail H" and "Polytail HA") having a hydroxyl group at the molecular end. Moreover, (b) polybutadiene polymer containing an allyl type hydroxyl group at the molecular end is specifically a viscous polymer having an average molecular weight of 2800, a hydroxyl value of 42 to 47 mgKOH, and a viscosity of about 50 poise at room temperature. A feature of this polybutadiene polymer is that it exhibits good reactivity with various substances because it contains an allyl type hydroxyl group at the end of the molecule. Furthermore, derivatives of this polybutadiene polymer are obtained by reacting a hydroxyl group at the end of the molecule with a compound having various functional groups, and specifically, Terminal carboxyl groups such as A derivative obtained by a condensation reaction between the hydroxyl group of and the molecular terminal hydroxyl group of the polybutadiene polymer, or the structural formula An example is an intramolecular epoxy compound of polybutadiene represented by Next, (c) a hydrocarbon polymer containing a carboxyl group at the end of the molecule and having a saturated or partially saturated main chain is specifically
A polymer synthesized by the production method described in No. 50-7894, that is, a living polymer is reacted with a halogenoalkylene oxide and/or a polyepoxide, the resulting polymer is reacted with a monoepoxide, and this is further reacted with an organic polymer. It is a polymer obtained by reacting with a carboxylic acid anhydride. The above-mentioned living polymer refers to a dialkali metal having a molecular weight of 500 to 10,000 and containing an alkali metal at both ends of the molecule obtained by reacting a conjugated diolefin and/or a vinyl compound with an alkali metal or an organic alkali metal by a well-known method. It is a polymer. In addition, halogenoalkylene oxide is a general formula such as epichlorohydrin. (wherein, , is an alkylene oxide containing one epoxy group in one molecule. Next, organic polycarboxylic acid anhydrides are aliphatic polycarboxylic acids such as maleic acid and succinic acid, aromatic polycarboxylic acids such as phthalic acid and pyromellitic acid, and alicyclic polycarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid. Anhydrides such as polycarboxylic acids. In the hydrocarbon polymer having the above composition, the molecular weight and the introduction ratio of carboxyl groups can be arbitrarily adjusted by appropriately adjusting the ratio of the living polymer to the halogenoalkylene oxide and/or polyepoxide.
Moreover, since the obtained polymer contains carboxyl groups, it has the characteristic that it can be reacted with various crosslinking agents to obtain a variety of compositions ranging from rubber-like elastic bodies to hard resins. . (3) Halogenating agent A halogenating agent is (a)

[Formula] A compound containing a bond (wherein X is a halogen); (b) an alkyl hypohalide; and (c) a hypohalite. In the above (a) molecule

[Formula] A compound containing a bond (wherein X is a halogen) is specifically a halogenated succinimide such as N-bromsuccinimide, an isocyanuric acid halide such as trichloroisocyanuric acid or dichloroisocyanuric acid, or dichlorodimethyl Examples include halogenated hydantoins such as hydantoins. (b) Alkyl hypohalide means normal, secondary or tertiary alkyl hypohalide, particularly stable tertiary alkyl hypohalide, specifically tertiary butyl or tertiary amyl chloride. or bromide. Next, (c) hypohalite is a sodium salt, potassium salt, or calcium salt of hypochlorous acid or hypobromite. In addition to the above-mentioned halogen compounds, examples of halogenating agents include chlorine, bromine, or aqueous solutions thereof; mixtures of hypohalites and organic acids (Japanese Patent Publication No. 57-52216); antimony pentafluoride (Japanese Patent Publication No. 57-52216); Aqueous solutions of alkali metals or alkaline earth metals, mixed solutions of sulfur fluoride and bromine (Japanese Patent Publication No. 53-27751); Mixtures of iodine and potassium iodide (Japanese Patent Publication No. 53-27751); Halogen oxygen acids Various halogen-containing substances can be used, such as a mixed aqueous solution of salt and concentrated hydrochloric acid (Japanese Patent Publication No. 46-22103); a mixed aqueous solution of alkali bromide and peroxodisulfuric acid. The adhesive composition of the present invention can be prepared by simply mixing the compounds having the compositions (1) to (3) above in a solvent at a predetermined ratio. That is, the halogenating agent is
It is preferable to mix in a proportion of 0.01 to 10 parts by weight; if the halogenating agent is less than 0.01 parts by weight, the adhesion will be poor, and if it exceeds 10 parts by weight, no effect of improving adhesion will be observed. Further, the mixing ratio of the hydrocarbon polymer (or its derivative) containing a functional group at the molecular terminal to the mixture of the unvulcanized rubber composition and the halogenating agent may be arbitrary. Next, the solvent used for the above mixing has a halogenating agent in its molecules.

[Formula] In the case of a compound containing a bond (wherein X is a halogen), aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as dioxane and tetrahydrofuran; methyl acetate, butyl acetate, isopropyl acetate Organic solvents appropriately selected from acetate esters such as; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; chlorinated hydrocarbons such as ethyl chloride, chloroform, and carbon tetrachloride, or a mixed solvent consisting of two or more of the above solvents. However, other organic solvents may be used as long as they do not react with the halogen compound. In addition, when using hypohalite, since water is the solvent, it is necessary to combine the unvulcanized rubber composition with a hydrocarbon polymer containing a functional group at the molecular end (or
When mixing with a derivative thereof, an emulsifier may be added to form a latex-like adhesive composition. Furthermore, in the case of an alkyl hypohalide, any of the above-mentioned various solvents and water may be used. Next, the amount of solvent to be added may be adjusted according to the viscosity depending on the method used to apply the adhesive composition to the surface of the polyolefin polymer base material, but the solid content concentration in the solution should be 30% or less. If it exceeds 30%, the stability of the mixture may decrease and solid content may precipitate. Furthermore, since the adhesive composition is a one-component type, it has a very long pot life, and if the viscosity increases due to evaporation of the solvent, the viscosity can be adjusted by adding a solvent again. It should be noted that no special equipment is required for the coating method, and ordinary coating methods such as dipping, brush coating, and spray coating may be employed. Next, the polyolefin polymer base material to which the above-mentioned adhesive composition is applied refers to the above-mentioned polyolefin synthetic resin and polyolefin vulcanized rubber, as well as the amount ( Usually 1/2 part by weight or less) and other rubber components (SBR,
Also includes those containing resin components (BR, IIR, CR, NBR, IR, etc.) and resin components (PP, PE, EVA, etc.). These polyolefin-based vulcanized rubbers also contain commonly used additives, such as sulfur, morpholine disulfide, dicumyl peroxide, etc. as vulcanizing agents, and 2-mercaptobenzothiazole as vulcanization accelerator. , zinc dimethyldithiocarbamate, tetramethylthiuram disulfide, anti-aging agents, antioxidants, ozone deterioration inhibitors such as phenyl-α-naphthylamine, 2,6-di-t-butyl-p-cresol, fillers, etc. Usually, carbon black, hydrated silicic acid, magnesium carbonate, clay, etc. are blended as plasticizers, and dioctyl sebacate, mineral oil, etc. are blended as plasticizers. EXAMPLES Hereinafter, the adhesive composition of the present invention will be described in detail with reference to Examples. Examples 1 to 6 below consist of a hydrocarbon polymer containing at least one hydroxyl group at the molecular end and having a saturated or partially saturated main chain, unvulcanized rubber, and a halogenating agent. This is an example of preparing an adhesive composition. (The hydrocarbon polymers used were "Polytail H" and "Polytail HA" manufactured by Mitsubishi Chemical Industries, Ltd.) Example 1 An adhesive composition was prepared by blending compounds having the composition shown in Table 1. (All parts in the table below are parts by weight.)

[Table] The compositions of the adhesive compositions of Examples 2 to 6 are shown in Tables 2 to 6, respectively.

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[Table] Next, in order to examine the adhesion strength of the adhesive compositions of Examples 1 to 6 above, an adhesion test was conducted using the following method. First, an EPDM compound having the composition shown in Table 7 was prepared.
A test piece with a thickness of 2 mm was prepared by vulcanization treatment at 160°C for 30 minutes.

[Table] Next, each of the above test pieces was immersed in the adhesive compositions of Examples 1 to 6 and air-dried for 30 minutes at room temperature, and then a urethane compound having the composition shown in Table 8 was soaked in dry nitrogen gas. A urethane paint obtained by reacting at 80°C for 3 hours was applied to each test piece and cured at room temperature for 24 hours.

[Table] After that, the adhesion strength of the urethane coating formed on the surface of each test piece was investigated by a goblin test.
As shown in Table 9, it was found that all of them exhibited sufficient adhesion.

[Table] Examples 7 to 21 below are preparation examples of adhesive compositions comprising a polybutadiene polymer containing an allyl-type hydroxyl group at the molecular end, unvulcanized rubber, and a halogenating agent. In addition, as the polybutadiene polymer, the following polymers were used. "R-45HT" (trade name of polybutadiene polymer manufactured by Idemitsu Petroleum Science Co., Ltd.; hereinafter the same applies) Hydroxyl group content 0.83 (meq/g), hydroxyl value 46.6 (mg)
KOH/g), a polybutadiene polymer containing terminal hydroxyl groups with an average molecular weight of 2800. "R-45M" Hydroxyl group content 0.75 (meq/g), hydroxyl value 42.1 (mg
KOH/g) A polybutadiene polymer containing terminal hydroxyl groups with an average molecular weight of 2800. "Poly bd HTP-4" At the end of the molecule, A polybutadiene polymer derivative containing. "Poly bd R-45EPT" At the end of the molecule,

A polybutadiene polymer derivative containing the formula: "Poly bd CBC" A compound type polybutadiene polymer made by mixing carbon black into the above "R-45HT". "Poly bd R-45EPI" structural formula, An intramolecular epoxy compound of polybutadiene polymer represented by "Poly bd R-45ACR" At the end of the molecule, A polybutadiene polymer derivative containing. "Poly bd R-45MA" Maleic acid ester derivative of the above "R-45HT". Example 7 An adhesive composition was prepared by blending compounds having the composition shown in Table 10.

[Table] Adhesive compositions of Examples 8 to 18 were prepared by blending compounds having the compositions shown in Tables 11 to 21 below.

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[Table] Example 15 100.0 parts of a 5% toluene solution of R-45HT with an emulsifier added and 1 part of trichloroisocyanuric acid.
% aqueous solution and 10.0 parts of SBR were mixed to prepare an adhesive composition. Example 16 100.0 parts of a 5% toluene solution of R-45HT with an emulsifier added and 2 parts of trichloroisocyanuric acid.
% aqueous solution and 10.0 parts of BR were mixed to prepare an adhesive composition. Example 17 An adhesive composition was prepared by mixing 100.0 parts of a 5% toluene solution of R-45HT with an emulsifier added, 100.0 parts of a 2% aqueous solution of sodium hypochlorite, and 10.0 parts of IIR. . Example 18 An adhesive composition was prepared by mixing 100.0 parts of a 5% toluene solution of R-45HT with an emulsifier added, 100.0 parts of a 10% aqueous solution of sodium hypochlorite, and 10.0 parts of NBR. . Next, a test similar to that for the adhesive compositions of Examples 1 to 6 was conducted using a 2 mm thick test piece obtained by vulcanizing the EPDM composition having the composition shown in Table 7 at 160°C for 30 minutes. As a result, as shown in Table 18,
It was found that all of them exhibited sufficient adhesion.

[Table] Examples 19 to 30 below are made from a hydrocarbon polymer containing a carboxyl group at the molecular end and whose main chain is saturated or partially saturated, unvulcanized rubber, and a halogenating agent. This is an example of preparing an adhesive composition. Example 19 A dilithium initiator was prepared by reacting naphthalene/metallic lithium/isoprene=2/40/30 (molar ratio) in diethyl ether. Living polybutadiene (molecular weight = 1250) was obtained by polymerizing 50 g of butadiene in cyclohexane using 0.04 mol of this dilithium initiator. To this living polybutadiene solution, 0.02 mol of a solution of epichlorohydrin in cyclohexane, then 0.08 mol of a solution of propylene oxide in tetrahydrofuran were added, and the reaction was completed by standing overnight. After that, 0.08 mol of a solution of phthalic anhydride in tetrahydrofuran was added and the mixture was kept at room temperature for 30 minutes. , and further reacted at 70°C for 3 hours. 2,6-di-t-butyl-p-cresol was added as a stabilizer to the obtained viscous liquid, and purified by reprecipitation in a toluene-methanol mixed solution according to a conventional method to obtain a carboxyl group-containing solution with an average molecular weight of 2800. Polymer-A
I got it. Next, 5 g of this carboxyl group-containing polymer A, 1 g of trichloroisocyanuric acid, and 10 g of EPDM were dissolved in 95 g of toluene to prepare an adhesive composition. Example 20 0.12 mol of a solution of vinylcyclohexene diepoxide in tetrahydrofuran was added to a solution of living polybutadiene (molecular weight = 1250) obtained by the same operation as in Example 15 above, and the reaction was completed by standing overnight. Add 0.08 mol of maleic acid in tetrahydrofuran and continue at room temperature for 30 minutes.
The reaction was carried out at 70°C for 3 hours. After adding a stabilizer to the obtained polymer and decomposing it with hydrochloric acid, a carboxyl group-containing polymer B having an average molecular weight of 1900 was obtained in a toluene-methanol mixed solution according to a conventional method. Next, 10 g of this carboxyl group-containing polymer-B, 1 g of trichloroisocyanuric acid, and 10 g of EPDM were dissolved in 90 g of toluene to prepare an adhesive composition. The adhesive compositions of Examples 21 to 30 were prepared by blending the compounds shown in Tables 19 to 28.

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[Table] Next, using a 2 mm thick test piece obtained by vulcanizing the EPDM composition having the composition shown in Table 11 at 160°C for 30 minutes, the adhesive compositions of Examples 1 to 6 were tested. As a result of conducting the same test as shown in Table 29, it was found that all of them exhibited sufficient adhesion.

[Table] The compositions of Comparative Examples 1 to 6 below are conventionally used as primer coating agents for polyolefin polymers. Comparative Example 1 A composition was prepared by diluting "Betucosol J-534" (manufactured by Dainippon Ink Chemical Industry Co., Ltd., linseed oil-modified long oil alkyd resin) with a mineral base and further adding cobalt naphthenate as a desiccant. Comparative Example 2 A composition was prepared by diluting "Orestar M55-80A" (manufactured by Mitsui Toatsu Co., Ltd., a moisture-curing polyurethane resin) with toluene. Comparative Example 3 A composition was prepared by diluting "Ester Resin-20" (manufactured by Toyobo Co., Ltd., saturated polyester resin) with a mixed solvent of methyl ethyl ketone/toluene = 1/9 (weight ratio). Comparative Example 4 A composition was prepared by diluting "Vinyrite-VMCH" (manufactured by Union Carbide, vinyl chloride-vinyl acetate copolymer) with a mixed solvent of methyl ethyl ketone/toluene = 1/1 (weight ratio). Comparative Example 5 "Esrex BM-2" (manufactured by Sekisui Chemical Co., Ltd., butyral resin) was mixed with butanol/xylene = 1/1.
A composition diluted with a mixed solvent of (weight ratio) was prepared. Comparative Example 6 1/1.5 (weight ratio) of "Desmofene-100" (manufactured by Bayer, polyhydroxy compound) and "Desmodyur-R" (manufactured by Bayer, polyisocyanate)
A composition was prepared by diluting a mixture consisting of the following with a mixed solvent of methylene glycol/butyl acetate/ethyl acetate/toluene=1/1/1/1 (weight ratio). Next, each of the compositions of Comparative Examples 1 to 6 was added to the
It was applied to a base material made of EPDM, and then a urethane paint having the composition shown in Table 8 above was applied, and after curing for 24 hours, the adhesion of the paint film was examined by a goblin test. The adhesion was extremely weak (0/100). Hereinafter, usage examples in which the above-mentioned adhesive composition is applied to various molded articles for automobiles will be explained. Usage Example 1 Glass Run The polyolefin vulcanized rubber for glass runs used in the sliding parts of the window glass of door sashes has the composition shown in Table 7, as an example. After extrusion molding of EPDM compound with the above composition, at 160℃
A glass run base material for automobiles was produced by vulcanization for 30 minutes. Next, the adhesive composition of Example 1 was applied to the surface of the same base material by dipping and air-dried for 30 minutes at room temperature, and then a urethane paint having the composition shown in Table 30 was applied and cured for an additional 24 hours at room temperature. Ta.

[Table] The urethane polymers in Table 30 above are:
Urethane obtained by reacting each of the compositions shown in Tables 31 and 32 below at 80° C. for 30 minutes in dry nitrogen gas was mixed in a ratio of 100/40 (weight ratio).

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[Table] Usage example 2 Weather strip A weather strip that seals the gap between the car body and the door is made by extruding an EPDM compound with the composition shown in Table 33 and then heating it at 200℃ for 5 minutes. It is manufactured by sulfurizing it.

[Table] Next, the adhesive composition of Example 1 was applied to the surface of this weather slip base material by dipping and air-dried for 30 minutes at room temperature. ℃ for 3 hours, and further added 24.8 parts of 1,6-hexanediol and 170 parts of dimethylformamide, and dried at 80℃ in dry nitrogen gas.
The urethane paint obtained by reacting for 20 minutes was applied on top and cured for 24 hours. Then dimethyl silicone oil (100,000 cSt)
A 5% toluene solution of was applied onto the urethane coating.

[Table] Usage Example 3 Electrostatic Flocking Product Some of the glass run products of Usage Example 1 above have electrostatic flocking processing using short fibers applied to the glass sliding area. The adhesive composition of Example 1 was applied to the surface of the glass run base material by dipping, and
Air dried for a minute. Next, a urethane adhesive obtained by reacting the formulation shown in Table 35 in dry nitrogen gas at 80°C for 30 hours was applied thereon to electrostatically flock a pile of nylon 66 short fibers, and then the urethane adhesive The adhesive was cured with hot air at 10°C for 3 minutes to obtain an electrostatic flocking product.

〔Test method〕

Test machine: KI type abrasion tester Test conditions: Friction element Glass (thickness 5 mm) Load: 3 kg Friction element cycle: 60 times/min Friction element stroke: 145 mm The base material was attached to the above testing machine, and the base material was tested under the above test conditions. rubbed the surface. As a result, a good result was obtained in which no exposure of the base material was observed even after repeated friction 50,000 times. Further, the abrasion resistance of the coating film of the substrate treated in Use Example 2 was tested using the following method. [Test method] Testing machine: Reciprocating abrasion tester Test conditions: Friction element: Glass (thickness: 5 mm) Friction element cycle: 60 times/min Friction element stroke: 145 mm The base material was attached to the above testing machine, and under the above test conditions The surface of the base material was rubbed. As a result, a good result was obtained in which no exposure of the base material was observed even after repeated friction 20,000 times. Next, we conducted a 180 degree bending test to check the followability of each of the base materials in Usage Examples 1 to 3 above, and each base material showed extremely good followability, with flexibility that is a characteristic of polyolefin vulcanized rubber. It has been found that the adhesive composition and flexibility are not impaired in any way even when the adhesive composition is applied. Usage Example 4 Resin Molding Moldings attached to the side surfaces of automobile bodies are attached to the body via double-sided adhesive tapes made of polyethylene foam or the like. Therefore, a molding was manufactured by extrusion molding a vinyl chloride resin having the formulation shown in Table 36 at 170°C, and the following tests were conducted using this molding.

[Table] (a) As shown in Fig. 1, the adhesive composition 4 of Example 1 is applied as a primer on one side of the tape 3 made of 5x polyethylene foam, and the adhesive composition 4 of Example 1 is applied thereon as an adhesive 5a. G-17 (manufactured by Konishi Co., Ltd., CR adhesive) was applied. Furthermore, a commercially available acrylic adhesive 6 for double-sided tape was applied to the back side of the tape 3. Next, the vinyl chloride resin molding 2 was attached to the acrylic-coated iron plate 1 via the double-sided adhesive tape 7a prepared in this way. (b) As the adhesive composition in (a) above, the adhesive composition of Example 2 was used. (Others are the same as in (a)) (c) As the adhesive composition in (a) above, the one in Example 3 was used. (Others are the same as (a)) (d) Next, as shown in Figure 2, adhesive composition 4 of Example 4 was applied as a primer on one side of tape 3 made of 5x polyethylene foam. On top of that, Dianal-882 (manufactured by Mitsubishi Rayon Co., Ltd., acrylic adhesive) was applied as adhesive 5b. Furthermore, a commercially available acrylic adhesive 6 for double-sided tape was applied to the back side of the tape 3. Next, the double-sided adhesive tape 7 prepared in this way
A vinyl chloride resin molding 2 was attached to the acrylic-coated iron plate 1 via b. (e) As the adhesive composition in (d) above, the adhesive composition of Example 5 was used. (Others are the same as in (d)) (f) As the adhesive composition in (d) above, the one in Example 6 was used. (Others are the same as in (d)) (g) As Comparative Example 1, as shown in FIG. 3, only G-17 was applied as the adhesive 5a to one side of a tape 3 made of 5x polyethylene foam.
(Others are the same as in (a)) (h) As Comparative Example 2, as shown in FIG. 4, only the above-mentioned Dianal-882 was applied as the adhesive 5b to one side of the tape 3 made of 5x polyethylene foam. (Others are the same as in (d)) Next, each of the moldings 2 of (a) to (h) above was subjected to a tensile shear test at a pulling speed of 30 mm/min, and the results shown in Table 37 were obtained.

[Table] From the above test results, it was found that the adhesion of the paint, adhesive, or pressure-sensitive adhesive applied to the coating film made of the above-mentioned adhesive composition was extremely strong. Effects of the Invention As detailed above, when applying various paints, adhesives, etc. to the surface of molded products made of polyolefin vulcanized rubber or polyolefin synthetic resin, the adhesive composition of the present invention can be used as an undercoat. By applying various paints, adhesives, etc.
Provides extremely strong adhesion. Furthermore, in the case of a molded article made of polyolefin vulcanized rubber, the flexibility and flexibility, which are characteristics of the same rubber, are not impaired. Therefore, the adhesive composition of the present invention has excellent properties that can be applied not only to the above-mentioned various molded articles for automobiles, but also to polyolefin-based vulcanized rubber and polyolefin-based synthetic resins that require strong adhesion, and other wide-ranging applications. This is a great invention.

[Brief explanation of drawings]

1 and 2 are cross-sectional views showing a mounting structure for a molding using the adhesive composition of the present invention as a primer, and FIGS. 3 and 4 show an example of a conventional mounting structure for a molding. FIG. 2...Mall, 4...Adhesive composition.

Claims (1)

[Scope of Claims] 1 (1) at least one unvulcanized rubber composition selected from the following (); and (2) a carbonized rubber composition containing at least one functional group selected from the following () at the molecular end. A hydrogen-based polymer or its derivative; (3)
An adhesive composition containing a halogenating agent as a main component. () Natural rubber, ethylene-propylene-diene copolymer rubber, ethylene-propylene-copolymer rubber, styrene-butadiene rubber, polybutadiene rubber, isobutylene-isoprene copolymer rubber, polychloroprene rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene Unvulcanized rubber () Hydroxyl group, allyl hydroxyl group, carboxyl group. 2. The adhesive composition according to claim 1, wherein the hydrocarbon polymer is a hydrocarbon polymer containing at least one hydroxyl group at a molecular end and having a saturated or partially saturated main chain. . 3. The adhesive composition according to claim 1, wherein the hydrocarbon polymer is a polybutadiene polymer containing an allyl hydroxyl group at the end of the molecule. 4. The adhesive composition according to claim 1, wherein the hydrocarbon polymer contains a carboxyl group at the molecular end and has a saturated or partially saturated main chain. 5. The halogenating agent is at least one of (a) a compound containing a bond of the formula (in the formula, X is a halogen) in the molecule, (b) an alkyl hypohalide, and (c) a hypohalite. The adhesive composition according to claim 1, which comprises one type of adhesive composition. 6. The adhesive composition according to claim 1, wherein the halogenating agent is mixed in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight of the solid content of the unvulcanized rubber composition.