JPH0426341B2 - - Google Patents

Description

[Detailed description of the invention]

Purpose of the Invention (Field of Industrial Application) The present invention relates to an adhesive composition that strengthens the adhesion of paints, adhesives, etc. applied to the surface of polyolefin polymers, such as polyolefin vulcanized rubber and polyolefin synthetic resins. It is related to. (Prior art) There are many types of industrial rubbers and synthetic resins, but especially polyolefin-based rubbers such as ethylene-propylene-diene terpolymer rubber (EPDM) and ethylene-propylene copolymer rubber (EPM). Vulcanized rubber or polyolefin-based synthetic resins such as polypropylene (PP) and polyethylene (PE) are natural rubber (NR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), and isobutylene-isoprene copolymer rubber ( Synthetic rubbers such as IIR), polychloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), and polyisoprene rubber (IR), or ABS resin, polystyrene resin (PS), acrylonitrile-styrene copolymer resin (AS) Compared to synthetic resins such as ethylene-vinyl acetate copolymer resin (EVA), it is a polymer with excellent properties such as excellent weather resistance, aging resistance, and ozone resistance. Nowadays, it has come to be used in many fields. (Problems to be Solved by the Invention) However, since polyolefin-based vulcanized rubbers such as EPDM and EPM, and polyolefin-based synthetic resins such as PP and PE do not contain polar groups in the main chain of their molecules, The disadvantage is that even if paint or adhesive is applied to the surface, the resulting coating film is likely to peel off. Therefore, it is currently extremely difficult to coat these polyolefin polymers, or to adhere them to each other or to metals. Although many countermeasures have been attempted in the past to address these drawbacks, no satisfactory solution has yet been found. As a result of repeated research on the adhesive properties of the above-mentioned polyolefin-based polymers, the present inventors have discovered an adhesive composition that has sufficient adhesion to the same polymer and various paints and adhesives, and have thus arrived at the present invention. It is. Structure of the Invention (Means for Solving Problems) That is, the present invention provides a polymer obtained by hydrogenating a copolymer of a conjugated diene compound and an aromatic compound containing a vinyl group, and

[Formula] The above problems can be solved by devising an adhesive composition comprising a mixture of the compound described in a below or at least one alkyl hypohalide containing a bond (wherein X is a halogen). It's a diagram. a Halogenated succinimides, halogenated isocyanuric acids, halogenated hydantoins (action) Since the above adhesive composition contains a halide, the conjugated diene compound and vinyl group in the same composition are activated by the halogen, which is a polar group. The polymer obtained by hydrogenating a copolymer of aromatic compounds containing (hereinafter referred to as saturated aliphatic ring-containing polymer) is activated and has excellent adhesion to polyolefin polymers and various paints and adhesives. It becomes a composition with sexual power. Further, by using the above-mentioned saturated aliphatic ring-containing polymer, it is possible to form an adhesive film that is rich in rubber elasticity and has high tensile strength. (Example) Each compound constituting the adhesive composition of the present invention will be described in detail below. What is a saturated aliphatic ring-containing polymer?
A conjugated diene compound as shown in Publication No. 71391,
Average molecular weight 500 to 50,000 obtained by hydrogenating a copolymer with an aromatic compound containing a vinyl group,
Preferably it is a polymer of 1,000 to 30,000. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene, and the aromatic ring-containing functional hydrocarbon polymer includes aromatic It is obtained by polymerizing monomers of the group monomer alone or together with other comonomers, and examples of specific production methods thereof include Japanese Patent Publication No. 37-8190, Japanese Patent Publication No. 38-342, and Japanese Patent Publication No. 38-38.
No. 5993, Special Publication No. 14747, Special Publication No. 42-22048
Examples include the manufacturing methods described in Japanese Patent Publication No. 47-36273. Furthermore, the above-mentioned aromatic ring refers to aromatic compounds such as styrene, vinyltoluene, vinylnaphthalene, phenylbutadiene, methylstyrene, divinylbenzene, coumaron, indene, vinylphenol, vinylbenzoic acid, or cinnamic acid, and derivatives thereof. These can be used alone or in combination of two or more. In addition to the above conjugated dienes, heterocyclic compounds,
Acrylic acid derivatives, methacrylic acid derivatives, fumaric acid derivatives, maleic acid derivatives, etc. may be blended as comonomers. The aromatic ring content in the aromatic ring-containing functional hydrocarbon polymer is usually 1 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the same polymer. The functional groups in the polymer include hydroxyl groups and carboxyl groups, and the content of the functional groups is 1 per polymer molecule.
or more, preferably 1.5 or more. The saturated aliphatic ring-containing polymer may be prepared by combining the aromatic ring-containing functional hydrocarbon polymer with a metal catalyst such as ruthenium, palladium, platinum, rhodium, or osmium alone, or with carbon black, alumina, diatomaceous earth, or carbonate. It is obtained by catalytic hydrogenation using a carrier such as barium, calcium carbonate, or silica, and the cured product of this saturated aliphatic ring-containing polymer has high rubber elasticity, high tensile strength, and weather resistance. It is a polymer that exhibits excellent properties such as water resistance, moisture resistance, ozone resistance, and heat resistance. Next, in the molecule

[Formula] Compounds having a bond (wherein X is a halogen) include halogenated succinimides such as N-bromsuccinimide, isocyanuric acid halides such as trichloroisocyanuric acid and dichloroisocyanuric acid, and furthermore, compounds such as dichlorodimethylhydantoin. Examples include halogenated hydantoins. Also, alkyl hypohalide is normal,
Secondary or tertiary alkyl hypohalides, especially stable tertiary alkyl chlorides, bromides, etc. Specifically, tertiary butyl hypochloride,
Tertiary butyl hypobromide, tertiary amyl hypochloride, tertiary amyl hypobromide and the like are particularly preferred, and halogen-substituted alkyl hypochloride such as dichloro, trichloro or fluoromethyl hypochloride may also be used. . The adhesive composition of the present invention contains a polymer obtained by hydrogenating a copolymer of a conjugated diene compound and an aromatic compound containing a vinyl group;

[Formula] It is obtained by mixing a compound described in a below containing a bond (wherein X is a halogen) or at least one alkyl hypohalide in a solvent. a Halogenated succinimides, halogenated isocyanuric acids, halogenated hydantoins The solvents used here are n-hexane,
Saturated hydrocarbons such as cyclohexane; benzene,
Aromatic hydrocarbons such as toluene and xylene; iso
- Alcohols such as propyl alcohol and n-butyl alcohol; Ethers such as diethyl ether and tetrahydrofuran; Acetate esters;
The solvent is a solvent appropriately selected from ketones or a mixed solvent of two or more thereof. Also, in the molecule

[Formula] The compound having a bond (wherein X is a halogen) is preferably mixed in a proportion of 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the saturated aliphatic ring-containing polymer. It is. On the other hand, the alkyl hypohalide is preferably mixed in an amount of 0.01 to 300 parts by weight, more preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the saturated aliphatic ring-containing polymer. These halogen compounds have no effect if the mixing ratio is less than the above-mentioned mixing ratio, and even if they are mixed in excess, no improvement in the effect is observed. The solid content concentration of the adhesive composition is preferably 30% or less; if it exceeds 30%, the stability of the mixture may deteriorate and the solid content may precipitate. Next, the method of using this adhesive composition is as follows:
This can be applied by dipping, spraying, brushing, etc.
It is sufficient to simply apply the coating to the surface of the polyolefin polymer molding using a conventional coating method. In addition, although this adhesive composition can be easily cured with a curing agent such as isocyanate or polycarboxylic acid, its pot life before adding the curing agent is very long, and the viscosity decreases due to evaporation of the solvent. If the viscosity rises, add solvent again to adjust the viscosity.
Can be reused. On the other hand, polyolefin polymers are
Polyolefin vulcanized rubber such as EPDM and EPM, or polyolefin synthetic resin such as PP and PE, but also rubber components such as NR, SBR, IIR, CR, NBR, etc. in amounts that do not lose their properties. Also includes those containing resin components such as ABS, PS, PE, PP, and EVA. Further, the content of these rubber components or resin components is usually 1/2 or less of that of EPDM, EPM, etc. The above polyolefin-based vulcanized rubber contains commonly used compounds, including sulfur, morpholine disulfide, and dicumyl peroxide as vulcanizing agents, and 2-mercaptobenzothiazole and zinc dimethyldithiocarbamate as vulcanization accelerators. , tetramethylthiuram disulfide, phenyl-α-naphthylamine, 2,6-di-t-
Butyl-p-cresol, carbon black, magnesium carbonate, clay as a filler, dioctyl sebacate, mineral oil, etc. as a plasticizer are added. Example 1 Create an argon atmosphere in the autoclave 1,
75 g of 3-butadiene, 25 g of styrene, 70 g of isopropyl alcohol, and 10 g of 60% hydrogen peroxide were charged, and a polymerization reaction was carried out at 90° C. for 5 hours to obtain a butadiene-styrene copolymer. Next, 50 g of this copolymer, 50 g of cyclohexane
g and carbon supported ruthenium (5%) catalyst 5
After charging g into an autoclave and purging the system with argon gas, hydrogen gas was filled in and the gas pressure was set to 50
The hydrogenation reaction was carried out for 8 hours under the conditions of Kg/cm ² and 100°C. After filtering off the catalyst, the generated hydrogenated product was precipitated in methanol to prepare a saturated aliphatic ring-containing polymer. Next, 5 g of the same saturated aliphatic ring-containing polymer and 1 g of trichloroisocyanuric acid were mixed in 95 g of toluene to prepare an adhesive composition. Example 2 In place of trichloroisocyanuric acid in the adhesive composition of Example 1, 1 N-bromsuccinimide was used.
(Others were the same as in Example 1). Example 3 The amount of trichloroisocyanuric acid in Example 1 was
The weight was 0.5 g (others were the same as in Example 1). Example 4 The amount of trichloroisocyanuric acid in Example 1 was reduced to 2
(Others were the same as in Example 1). Example 5 1,3-butadiene 64 was prepared in the same manner as in Example 1.
g, styrene 36g, isopropyl alcohol 70g
and 8 g of 60% hydrogen peroxide solution at 120℃, 2
A time polymerization reaction was performed to obtain a butadiene-styrene copolymer. Next, this copolymer was hydrogenated in the same manner as in Example 1 to prepare a saturated aliphatic ring-containing polymer. Next, 10 g of the same saturated aliphatic ring-containing polymer and 1 g of trichloroisocyanuric acid were mixed in 90 g of toluene to prepare an adhesive composition. Example 6 In 95 g of toluene, 5 g of the saturated aliphatic ring-containing polymer prepared in Example 1 and 1 g of tertiary butyl hypochloride were mixed to prepare an adhesive composition. Example 7 The amount of tertiary butyl hypochloride in Example 6 was changed to 0.5 g (others are the same as Example 1). Example 8 The amount of tertiary butyl hypochloride in Example 6 was changed to 2 g ( (Others are the same as Example 1.) Example 9 The amount of tertiary butyl hypochloride in Example 6 was changed to 5 g (Others are the same as Example 1.) Example 10 In 90 g of methyl ethyl ketone, Example 5 was added. An adhesive composition was prepared by mixing 10 g of the saturated aliphatic ring-containing polymer prepared in step 1 with 3 g of tertiary butyl hypochloride. Example 11 In 90 g of toluene, 10 g of the saturated aliphatic ring-containing polymer prepared in Example 1, 1 g of tertiary butyl hypochloride, and 1 g of trichloroisocyanuric acid were mixed to prepare an adhesive composition. Example 12 In place of trichloroisocyanuric acid in Example 11, 1 g of N-bromsuccinimide was used (otherwise the same as in Example 11). Next, in order to examine the effects of the adhesive compositions of Examples 1 to 12 above, an adhesion test was conducted using the following method. First, a rubber compound having the composition shown in Table 1 was prepared at 160%
℃ for 30 minutes to produce a 2 mm thick base material made of EPDM.

【table】

[Table] After dipping each of the above EPDM base materials into the adhesive compositions of Examples 1 to 12 and air-drying them at room temperature for 30 minutes, a urethane formulation having the composition shown in Table 2 was placed in dry nitrogen gas. A urethane paint obtained by reacting at 80° C. for 3 hours was applied onto these and cured at room temperature for 24 hours.

[Table] After that, the adhesion of the coating film on each base material was examined by a cross-cut test, and it was found that all the base materials exhibited sufficient adhesion (100/100). The compositions of Comparative Examples 1 to 3 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 & Chemicals, a 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, 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). Next, the compositions of Comparative Examples 1 to 3 were added to the EPDM.
A urethane paint having the composition shown in Table 2 above was applied onto the base material, and after curing for 24 hours, the adhesion of the paint film was examined by a goblin test, but no adhesion was found in either case. Nakatsuta (0/
100). Next, 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 sliding parts with the window glass of door sashes has the composition shown in Table 1, as an example. After extrusion molding of EPDM compound with this composition, 160℃
The mixture was vulcanized for 30 minutes to produce a glass run base material for automobiles. Next, the adhesive composition of Example 1 was coated on the surface of this substrate by dipping and air-dried at room temperature for 30 minutes, and then a urethane paint having the composition shown in Table 3 was coated and cured at room temperature for an additional 24 hours.

[Table] The urethane prepolymers in Table 3 are made by reacting the compositions of Tables 4 and 5 at 80°C for 30 minutes in dry nitrogen gas, and each of the resulting urethanes. It was prepared by mixing at a ratio of 100/40 (weight ratio).

【table】

[Table] Usage example 2 Door weather strip The weather strip that seals the gap between the car body and the door is an example of a weather strip with the composition shown in Table 6.
It was manufactured by extruding an EPDM compound and then vulcanizing it at 200°C for 5 minutes.

[Table] Next, the adhesive composition of Example 1 was applied by dipping to the surface of this weatherstrip base material and air-dried for 30 minutes at room temperature. ℃ for 3 hours, and then 1,6
- A urethane paint obtained by adding 24.8 parts of hexanediol and 170 parts of dimethylformamide and reacting in dry nitrogen gas at 80°C for 20 minutes was applied thereon and left for 24 hours to form an adhesive film and urethane paint. hardened. Thereafter, a 5% solution of dimethyl silicone oil (100,000 cSt) in toluene was applied onto the urethane coating.

【table】

[Table] Usage Example 3 Electrostatic flocking products Some of the glass run products in Usage Example 1 have electrostatic flocking done using short fibers on the glass sliding parts. The adhesive composition of Example 1 was applied by dipping onto the surface of this glass run base material and air-dried for 30 minutes at room temperature. Next, a urethane adhesive obtained by reacting the formulation shown in Table 8 at 80°C in dry nitrogen gas for 3 hours was applied thereon, and a pile of nylon 66 staple fibers was electrostatically flocked thereon. 100 glue
An electrostatic flocked product was obtained by curing with hot air at ℃ for 3 minutes.

[Table] Next, the abrasion resistance of the coating films of the substrates treated in Use Examples 1 and 3 was tested using the following method. Testing 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 conditions described above. The surface of the material was rubbed. As a result, we obtained the good result that no exposure of the base material was observed even after repeated friction 50,000 times.In addition, regarding the wear resistance of the coating film of the base material treated in Use Example 2, The test was conducted in the following manner. Testing machine: Reciprocating wear 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 the base material surface was inspected under the conditions described above. 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. Also, regarding the followability of each base material in usage examples 1 to 3.
A 180 degree bending test was conducted, and all showed extremely good followability, with no loss of flexibility and flexibility, which are characteristics of polyolefin vulcanized rubber. 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 as a base material. Therefore, a molding was manufactured by extrusion molding a vinyl chloride resin having the formulation shown in Table 9 at 170°C, and the following tests were conducted using this molding.

[Table] (a) As shown in Figure 1, the adhesive composition 4 of Example 1 and G-17 (manufactured by Konishi, CR type) were applied to one side of the tape 3 made of 5x polyethylene foam. Adhesive) and a commercially available acrylic adhesive 6 for double-sided tapes are applied to the untreated side to prepare a double-sided adhesive tape 7a, and the vinyl chloride resin molding 2 is coated with acrylic via this double-sided adhesive tape 7a. Pasted on iron plate 1. (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 adhesive composition of Example 5 was used (others were the same as in (a)). (d) Next, as shown in FIG. 2, adhesive composition 4 of Example 1 and DIANAL 882 (manufactured by Mitsubishi Rayon, acrylic adhesive) were applied to one side of tape 3 made of polyethylene foamed 5 times. agent) and a commercially available acrylic adhesive for double-sided tape 6 on the untreated side to prepare a double-sided adhesive tape 7b.
A vinyl chloride resin molding 2 was attached to the acrylic-painted iron plate 1 via b. (e) As the adhesive composition in (d) above, the adhesive composition of Example 6 was used (others are the same as in (d)). (f) As the adhesive composition in (d) above, the adhesive composition of Example 11 was used (others are the same as in (d)). (g) As Comparative Example 1, as shown in FIG. 3, only the above G-17 was applied as the adhesive 5a on one side of the 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 Dial 882 was applied as the adhesive 5b to one side of the tape 3 made of 5x polyethylene foam. (Others are the same as (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 10 were obtained.

[Table] From the above test results, it was found that the adhesion of the paint and adhesive applied to the surface of the adhesive composition was extremely strong. Effects of the Invention As detailed above, the adhesive composition of the present invention is used as an undercoat when applying various paints and adhesives to the surface of molded products made of polyolefin vulcanized rubber or polyolefin synthetic resin. By applying various paints and adhesives on top of it, extremely strong adhesion can be obtained. Furthermore, in the case of polyolefin-based vulcanized rubber, the flexibility and flexibility, which are the characteristics of the same rubber, are not impaired. Therefore, this adhesive composition is an excellent invention that can be applied to a wide range of applications, including the various molded articles for automobiles mentioned above, as well as polyolefin vulcanized rubber and polyolefin synthetic resins that require strong adhesion. be.

[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 each show an example of a conventional mounting structure for a molding. FIG. 2...Mall, 4...Adhesive composition.

Claims (1)

[Scope of Claims] 1 A polymer obtained by hydrogenating a copolymer of a conjugated diene compound and an aromatic compound containing a vinyl group, and a polymer containing a [formula] bond (in the formula, X is a halogen) in the molecule An adhesive composition comprising a mixture of the compound described in a below or at least one alkyl hypohalide. a Halogenated succinimides, halogenated isocyanuric acids, halogenated hydantoins 2 The polymer obtained by hydrogenating the copolymer of the conjugated diene compound and an aromatic compound containing a vinyl group is a butadiene-styrene copolymer. An adhesive composition according to claim 1.