JPH0446227B2 - - Google Patents

Description

[Detailed description of the invention]

Purpose of the Invention (Field of Industrial Application) The first and second inventions provide a laminate in which a polyolefin polymer such as a polyolefin vulcanized rubber or a polyolefin synthetic resin and a polar polymer are laminated via an adhesive layer. It is related to. (Prior technology) There are many types of industrial rubber products, but polyolefin vulcanized rubbers such as ethylene-propylene-diene ternary copolymer rubber (EPDM) and ethylene-propylene copolymer rubber (EPM) are particularly popular. It exhibits outstanding performance in terms of weather resistance, aging resistance, ozone resistance, etc., and the operating temperature range is -50℃ to 150℃.
Rubber has excellent features such as a wide range of properties, so it is used in many ways as a base material for various laminates and molded products. In addition, depending on the application, the above
Natural rubber (NR) and styrene in EPDM and EPM
Butadiene copolymer rubber (SBR), butadiene rubber (BR), isobutylene-isoprene copolymer rubber (IIR), chloroprene rubber (CR), acrylonitrile-butadiene copolymer rubber (NBR), isoprene rubber (IR), chlorosulfonation Rubbers that are blended with synthetic rubbers such as polyethylene (CSM) and acrylic rubber (ACM), or rubbers that are blended with resins such as ABS resin, styrene resin (PS), polyethylene (PE), and polypropylene (PP) are also used in many fields. It is used. On the other hand, polyolefin-based synthetic resins such as PP and PE mentioned above also exhibit excellent performance in terms of weather resistance, aging resistance, and ozone resistance, as well as polyolefin-based vulcanized rubber, and are also inexpensive, so they are used in various vehicles. It is used in a wide range of applications as a base material for various laminates and molded bodies, such as parts and electrical products. (Problem to be solved by the invention) However, 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. polymer i.e.
NR, SBR, BR, IIR, CR, NBR, IR, CSM,
Synthetic rubber such as ACM, ABS resin, PS,
Less reactive than synthetic resins such as vinyl chloride resin (PVC) and nylon resin. Therefore, even if a laminate is manufactured by inserting a molded body made of the polyolefin polymer and extrusion molding or injection molding the polar polymer, there may be a difference in the heat shrinkage rate of the two or a difference in the plasticizer blended into the polymer. There was a problem in that peeling occurred on the bonded surface due to migration. Further, even if a paint or adhesive is applied to strengthen the adhesion of the bonded surfaces, there is a problem in that the resulting coating film peels off and, as a result, the bonded surfaces peel off for the reasons mentioned above. Although many countermeasures have been attempted to address the above-mentioned problems, no satisfactory solution has yet been found. As a result of repeated research in view of the above problems, the present inventors have arrived at the present invention by discovering an adhesive that has strong adhesion to both polyolefin polymers and polar polymers. It is. Structure of the Invention (Means for Solving the Problems) That is, the first invention is a molded article formed by laminating a polyolefin polymer and a polar polymer, in which chlorinated polypropylene and polyurethane are added to the joint surface of the two polymers. This laminate is characterized by being coated with an adhesive layer made of a mixture of the following. Further, the second invention provides a molded article in which a polyolefin polymer and a polar polymer are laminated, and an adhesive layer made of a mixture of chlorinated polypropylene, polyurethane, and a halogenating agent is coated on the joint surface of the two polymers. It employs a laminate that is characterized by: (Function) The adhesive layer made of a mixture of chlorinated polypropylene and polyurethane in the first invention and the adhesive layer made of a mixture of chlorinated polypropylene, polyurethane and a halogenating agent in the second invention are made of a polyolefin polymer and a polar polymer. Since it has strong adhesion to both, the bonding surfaces of the laminate coated with the adhesive layer having such a composition will be firmly adhered to each other for a long period of time. (Example) Prior to the description of the example, each structure of the laminate will be described. First of all, polyolefin polymers are
These are polyolefin-based vulcanized rubbers such as EPDM and EPM, and polyolefin-based synthetic resins such as PP and PE. Furthermore, depending on the application, the above EPDM or EPM
The above-mentioned natural rubber, various synthetic rubbers, or ABS
It also includes vulcanized rubber that is a blend of resins, such as resins, PS, PE, and PP. On the other hand, polar polymers include the aforementioned NR, SBR, BR,
Various rubbers that contain polar groups in their molecules, such as IIR, CR, NBR, and IR ACM, or various synthetic resins that contain polar groups in their molecules, such as ABS resin, PS, PVC, and nylon resin. . The laminates of the first invention and the second invention are both molded products formed by laminating the above-mentioned polyolefin polymer and polar polymer, and are formed by various methods such as extrusion molding, injection molding, press molding, or vacuum forming. A desired shape is given by the molding method. Next, the adhesive layer of the first invention is made by applying an adhesive prepared by diluting a mixture of chlorinated polypropylene and polyurethane with a solvent to the above polyolefin polymer and/or the adhesive layer.
Alternatively, it can be obtained by applying it to the surface of a polar polymer and then drying it naturally or by heating. The chlorinated polypropylene used here is preferably a chlorinated polypropylene with a degree of chlorination of 5 to 60%, considering its adhesion to polyolefin polymers and compatibility with polyurethane. Polyurethane is produced by polymerizing polyol and isocyanate in a molar ratio such that the isocyanate is in excess, then adding a chain extender and further polymerizing the product.
A two-component curing polyurethane containing a group or an OH group is preferred. The polyol may be either a polyester polyol or a polyether polyol, and the glycol component of the polyester polyol may include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol,
1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol,
Trimethylolpropane can be exemplified. Examples of the organic acid component to be reacted with the glycol component include dicarboxylic acids such as succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, maleic acid, adipic acid, azelaic acid, and sebacic acid. On the other hand, examples of polyether polyols include polyoxypropylene diol, polytetramethylene glycol ether, and polyoxyethylene diol. As the chain extender, those exemplified as the glycol component of the polyester polyol may be used. It should be noted that various polyols other than those exemplified above can be used, such as chloroprene rubber and acrylic resin, but if the plasticizer contained in the polar polymer migrates to the joint surface, the adhesion strength tends to decrease. Therefore, it is particularly preferable to use a polyester polyol that is not easily affected by this plasticizer. Next, polyisocyanate is 2,4-tolylene diisocyanate, hydrogenated 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 1,5 - Diisocyanates such as naphthalene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, or 4,4',4''-triphenylmethane triisocyanate, tris-
It is a polymer obtained by polymerizing a polyfunctional isocyanate such as (p-isocyanate phenyl)-thiophosphate. A preferred blending ratio of the chlorinated polypropylene and polyurethane is 1 to 250 parts by weight of polyurethane per 100 parts by weight of chlorinated polypropylene, and if the blending ratio of polyurethane is less than the above range, it will not contribute to improving adhesion. Further, even if the amount of polyurethane exceeds 250 parts by weight, no improvement in adhesion can be expected, and moreover, the pot life will be shortened. In addition, in the mixture of the chlorinated polypropylene and polyurethane, if necessary, a diisocyanate, a polyfunctional isocyanate, or a low-molecular polyol such as trimethylolpropane, glycerin, or pentaerythritol may be added to 100 parts by weight of the chlorinated polypropylene. By adding in an amount not exceeding 50 parts by weight, the adhesion can be further improved. Next, the adhesive layer of the second invention is prepared by applying an adhesive prepared by diluting a mixture of chlorinated polypropylene, polyurethane, and a halogenating agent with a solvent to the surface of the polyolefin polymer and/or polar polymer, and then drying it naturally or Obtained by heating and drying. The chlorinated polypropylene and polyurethane used here are the same as those used in the first invention. In addition, halogenating agents are

Typical examples include compounds containing [Formula] (wherein X represents halogen), alkyl hypohalides, or hypochlorites, but there are also chlorine, bromine, or aqueous solutions thereof; hypochlorous acid. A mixture consisting of a salt and an organic acid (Special Publication 1983-
52216); Antimony pentafluoride (Special Publication 1972-
23483); aqueous solutions of alkali metals or alkaline earth metals; mixed solutions consisting of sulfur fluoride and bromine (Japanese Patent Publication No. 53-27751); mixtures consisting of iodine and potassium iodide (Japanese Patent Publication No. 53-27751); halogen oxygen acids Mixed aqueous solution consisting of salt and concentrated hydrochloric acid
-22103); Various halogen compounds can be used, such as a mixed aqueous solution consisting of alkali bromide and peroxodisulfuric acid. in the molecule

[Formula] (wherein, X represents a halogen) Compounds specifically include halogenated succinimides such as N-brom succinimide;
Examples include isocyanuric acid halides such as dichloroisocyanuric acid and trichloroisocyanuric acid; and halogenated hydantoins such as dichlorodimethylhydantoin. Also, alkyl hypohalide is normal,
Among various secondary or tertiary alkyl hypohalides, it is particularly preferable to use stable tertiary alkyl hypochloride or tertiary alkyl hypobromide. Furthermore, examples of hypochlorite include sodium hypochlorite, potassium hypochlorite, and calcium hypochlorite, but when using these water-soluble halogenating agents, add an emulsifier. Must be used as an emulsion. Note that these various halogen compounds may be used alone or in combination of two or more. In addition, the preferred blending ratio of chlorinated polypropylene, polyurethane, and halogenating agent is 1 to 1 to 100 parts by weight of polyurethane per 100 parts by weight of chlorinated polypropylene.
The ratio is 250 parts by weight and the halogenating agent is 0.002 to 40 parts by weight, and if the halogenating agent is less than 0.002 parts by weight, it will not contribute to improving the adhesion. Further, even if the blending ratio is 40 parts by weight or more, no improvement in adhesion can be expected. The organic solvents used in the first and second inventions include saturated hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as dioxane and tetrahydrofuran; ethyl acetate and propyl acetate. Acetate esters such as acetone, cyclohexanone, ketones such as methyl ethyl ketone; methylene chloride, trichloroethylene,
A chlorinated hydrocarbon such as 1,1-trichloroethane; a solvent appropriately selected from dimethyl sulfoxide, dimethyl formamide, etc., or a mixed solvent consisting of two or more of these; however, it does not react with a halogenating agent or isocyanate. Other organic solvents may be used if they do not. Example 1 Polyester polyol (or polyether polyol) in a mixed solvent of 1,1,1-trichloroethane/dimethylformamide = 100/60
and isocyanate to a solid content of 35%, reacted in dry nitrogen gas at 80°C for 3 hours, added a chain extender and reacted at 80°C for another 3 hours to prepare polyurethane. did. The compositions and blending ratios (in terms of weight ratio) of the polyester polyol (or polyether polyol), isocyanate, and chain extender used are shown in Tables 1 to 7 below. (All parts in the table below are parts by weight.)

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Next, the above polyurethane and chlorinated polypropylene were mixed in a mixed solvent of 1,1,1-trichloroethane/dimethylformamide=100/60 to prepare an adhesive. Table 8 shows the mixing ratio (in terms of weight ratio) of the polyurethane and chlorinated polypropylene used.

【table】

【table】

[Table] Next, a resin plate is manufactured by extrusion molding polypropylene resin, and the adhesive-1 shown in Table-8 above is applied to the surface of the resin plate.
After coating No. 9 to 9, hot air at 80° C. was blown onto the surface for 10 seconds to dry the coating film to the touch. Next, this resin plate and a vinyl chloride resin having the composition shown in Table 9 below were co-extruded to produce a plate-shaped laminate.

[Table] After manufacturing the laminate consisting of the above polypropylene resin, adhesive layer and vinyl chloride resin, it was left at room temperature for 7 days, and then left in a constant temperature bath at 80°C for 1 hour, and then the adhesion of the bonded surfaces was examined. A peel test was conducted in the following manner. Test method: Tensilon universal tensile tester (manufactured by Toyo Baldwin Co., Ltd.) Tensile speed: 30 mm/min As a result, the adhesive layers made of adhesives-1 to 9 all had good adhesion to polypropylene resin and vinyl chloride resin. It was possible to obtain large tensile shear strength. Comparative Example 1 listed in Table 8 used an adhesive made only of chlorinated polypropylene, and its tensile shear strength was low compared to the adhesives 1 to 9 above. In addition, in Comparative Example 2, the mixing ratio of polyurethane to chlorinated polypropylene was excessive, and in Comparative Example 3, the mixing ratio of isocyanate to chlorinated polypropylene was excessive.
-9, its tensile shear strength was small. Next, the compositions of Comparative Examples 4 to 12 below are conventionally used as adhesives for polyolefin polymers. Comparative Example 4 A composition was prepared by diluting "Betucosol J-534" (manufactured by Dainippon Ink & Chemicals, Co., Ltd., linseed oil modified long oil alkyd resin) with a mineral base and further adding cobalt naphthenate as a desiccant. Comparative Example 5 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 6 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 7 "Eslec 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 8 A composition was prepared by diluting "Orestar M55-80A" (manufactured by Mitsui Toatsu Co., Ltd., a moisture-curing polyurethane resin) with toluene. Comparative Example 9 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). Comparative Example 10 4/1 of "Betsukosol J-524" (manufactured by Dainippon Ink & Chemicals, Co., Ltd., linseed oil modified long oil alkyd resin) and "Super Betsukamine J-820" (manufactured by Dainippon Ink & Chemicals, Ltd., butylated melamine resin) A composition was prepared by diluting the mixture with xylol. Comparative Example 11 A composition was prepared by diluting a 99/1 mixture of "Acryloid C-110V" (manufactured by Rohm & Haas, thermoplastic acrylic resin) and nitrocellulose with toluene. Comparative Example 12 "Acryloid C-110V" (manufactured by Rohm & Haas, thermoplastic acrylic resin) and nitrocellulose diluted with toluene. " (manufactured by Dainippon Ink & Chemicals Co., Ltd., thermosetting acrylic resin) and "Super Beckamine 47-508" were diluted with a mixed solvent of toluene and butyl acetate to prepare a composition. Each of the adhesives of Comparative Examples 4 to 12 above was applied to the surface of the polypropylene resin plate, and after drying to the touch, the vinyl chloride resin shown in Table 9 was co-extruded to produce a plate-shaped laminate. A peel test was conducted under the conditions described above to examine the adhesion of the joint surfaces of each laminate, but the adhesion was weak and extremely weak when compared to the cases where adhesives 1 to 9 were used. Only a small tensile shear strength was obtained. Example 2 The back side of the flocked cloth was lined with a sheet made of urethane resin foamed 30 times. On the other hand, the surface of the extruded polypropylene resin plate used in Example 1 was After applying the adhesives 1 to 9 on the surface, hot air at 80°C was blown onto the surface for 10 seconds to dry the coating film to the touch.Furthermore, this resin plate and the sheet made of the urethane resin were laminated, A plate-shaped laminate was manufactured by press forming at a pressure of 10 kg/cm ^2. Next, this laminate was left at room temperature for 7 days, and then in a constant temperature bath at 80°C for 1 hour. The tensile shear strength was measured under the same conditions using the Tensilon universal tensile tester of Example 1 to examine the adhesion of the adhesives.As a result, the adhesive layers made of adhesives 1 to 9 were all made of polypropylene resin. It exhibited good adhesion to the polypropylene resin and urethane resin, and was able to obtain large tensile shear strength.On the other hand, each of the adhesives of Comparative Examples 4 to 12 was applied to the surface of the polypropylene resin plate, and the Layering sheets made of urethane resin, 10
A plate-shaped laminate was produced by press molding at a pressure of Kg/cm ² . Then, in order to examine the adhesion strength of the joint surfaces of each laminate, the tensile shear strength was measured under the same conditions using the tester described above. However, its adhesion was weak and only extremely low tensile shear strength could be obtained. Next, after applying adhesives 1 to 9 on the surface of the extruded polypropylene resin plate, the base material of the sheet was changed from the urethane resin foam to a chloroprene rubber foam, and a plate-shaped laminate was formed by press molding. was manufactured. In addition, instead of the extrusion molded board made of polypropylene resin described above, extrusion molded boards are manufactured using ABS resin and polyamide resin, and after applying adhesives 1 to 9 on their surfaces, the base material of the sheet is made of polyethylene resin foam. Instead, a plate-shaped laminate was manufactured by press molding. The tensile shear strength of these laminates was also measured under the same conditions, and as a result, good adhesion was exhibited in all cases, and large tensile shear strength could be obtained. Example 3 The polyurethane and chlorinated polypropylene used in Examples 1 and 2 above were mixed in a mixed solvent of 1,1,1-trichloroethane/dimethylformamide = 100/60, and a halogenating agent was further added and mixed. The adhesive was adjusted by Table 10 shows the mixing ratio (weight ratio) of the polyurethane, chlorinated polypropylene, and halogenating agent used. Next, adhesives 10 to 10 of Table 10 were applied to the surface of the polypropylene resin extrusion molded plate used in Example 1.
19 was applied to the surface, and the surface was blown with hot air at 80℃ for 10 seconds to dry the coating film to the touch.The resin plate was then inserted and a vinyl chloride resin having the composition shown in Table 9 was injection molded. A plate-shaped laminate was produced. Next, this laminate was left at room temperature for 7 days, and then left in a constant temperature bath at 80°C for 1 hour, and then tested under the same conditions using the Tensilon universal tensile tester described above to examine the adhesion of the bonded surfaces. Tensile shear strength was measured. As a result, the adhesive layers made of Adhesives-10 to 19 all exhibited good adhesion to polypropylene resin and vinyl chloride resin, and were able to obtain large tensile shear strength. On the other hand, in the case of the laminates having adhesive layers made of each of the adhesives of Comparative Examples 4 to 12, the adhesion was weak and only extremely low tensile shear strength was obtained. In addition, in Comparative Example 13 listed in Table 10, the mixing ratio of the halogenating agent to the chlorinated polypropylene was excessive, so the tensile shear strength was low. Example 4 After applying the adhesives 10 to 19 on the surface of a 1.5 mm thick polypropylene resin sheet, blow hot air at 80°C on the surface for 10 seconds to dry the coating film to the touch, and then apply the adhesives 10 to 19 on the surface of a 1.5 mm thick polypropylene resin sheet. A laminated sheet was produced by laminating polyamide resin sheets together and vacuum forming them. Next, this laminated sheet was left at room temperature for 7 days,
Further, after being left in a constant temperature bath at 80° C. for 1 hour, the tensile shear strength was measured under the same conditions using the Tensilon universal tensile tester described above in order to examine the adhesion of the bonded surfaces. As a result, the adhesive layers made of Adhesives-10 to 19 all exhibited good adhesion to polypropylene resin and polyamide resin, and were able to obtain large tensile shear strength. In addition, in the case of the laminates having adhesive layers made of each of the adhesives of Comparative Examples 4 to 12, the adhesion was weak and only an extremely small tensile shear strength was obtained. In this way, in a molded article formed by laminating various polyolefin polymers and a polar polymer, adhesives-1 to 9 are applied to the joint surfaces of the polymers.
By applying and forming an adhesive layer consisting of (Examples 1 and 2) or adhesives -10 to 19 (Examples 3 and 4), a laminate whose bonded surfaces are firmly adhered for a long period of time can be obtained. Can be done. Effects of the Invention As detailed above, an adhesive layer made of a mixture of chlorinated polypropylene and polyurethane (first invention) or a mixture of chlorinated polypropylene and polyurethane is applied to the bonding surface of a molded product made of a polyolefin polymer and a polar polymer. Any laminate formed by coating an adhesive layer (second invention) made of a mixture with a halogenating agent exhibits an excellent effect in that the bonded surfaces thereof are firmly adhered for a long period of time. Therefore, the laminates of the first and second inventions can be used for automotive weather strips, glass runs, flocked products, or moldings with a resin tape attached to the back surface, which are made of a polyolefin polymer and a polar polymer. This is an excellent invention that can be embodied in various laminates.

Claims (1)

[Scope of Claims] 1. In a molded article formed by laminating a polyolefin polymer and a polar polymer, an adhesive layer made of a mixture of chlorinated polypropylene and polyurethane is coated on the joint surface of the two polymers. A laminate featuring: 2 The degree of chlorination of the chlorinated polypropylene is 5 to 5.
Claim 1 characterized in that 60%
Laminated body as described in section. 3. The laminate according to claim 1, wherein the polyurethane is a polyester polyurethane containing an NCO group or an OH group at the end of the molecule. 4. The laminate according to claim 1, wherein the adhesive layer is a mixture of 100 parts by weight of chlorinated polypropylene and 1 to 250 parts by weight of polyurethane. 5. A molded article formed by laminating a polyolefin polymer and a polar polymer, characterized in that an adhesive layer made of a mixture of chlorinated polypropylene, polyurethane, and a halogenating agent is coated on the joint surface of the two polymers. laminate. 6 The degree of chlorination of the chlorinated polypropylene is 5 to 5.
Claim 5 characterized in that 60%
Laminated body as described in section. 7. The laminate according to claim 5, wherein the polyurethane is a polyester polyurethane containing an NCO group or an OH group at the end of the molecule. 8. The halogenating agent is selected from the group consisting of (a) a compound containing [formula] (wherein X is a halogen) in the molecule, (b) an alkyl hypohalide, (c) a hypohalite, 6. The laminate according to claim 5, wherein the laminate is at least one of: 9. Claim 5, wherein the adhesive layer is a mixture of 100 parts by weight of chlorinated polypropylene, 1 to 250 parts by weight of polyurethane, and 0.002 to 40 parts by weight of a halogenating agent. Laminated body as described in section.