JPH0462538B2 - - Google Patents

Description

[Detailed description of the invention]

Object of the Invention (Field of Industrial Application) The present invention relates to a laminate formed by laminating a polyolefin polymer such as a polyolefin vulcanized rubber or a polyolefin synthetic resin and a polar polymer via an adhesive layer. (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 (CSD) 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. has been done. On the other hand, like polyolefin vulcanized rubber, polyolefin synthetic resins such as PP and PE have excellent weather resistance, aging resistance, ozone resistance, etc., and are also inexpensive, making them suitable for various vehicle parts. It is used in a wide range of applications as a base material for various laminates and molded products, such as in electronic products and electronic 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, NER, 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 extrusion molding or injection molding the polar polymer using a molded body made of the polyolefin polymer as an insert, there will be a difference in the heat shrinkage rate between the two and migration of the plasticizer blended into the polymer. There was a problem that peeling occurred on the bonded surface due to such factors. 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 and polar polymers. be. Structure of the Invention (Means for Solving Problems) That is, the present invention provides a molded article in which a polyolefin polymer and a polar polymer are laminated, and the joint surface of both the polymers includes (a) rubber; (b) Adhesive layer made of a mixture of polyurethane and polyisocyanate; or (b) Adhesive layer made of a mixture of rubber, polyurethane, and a halogenating agent. It is something. (Function) The mixture of rubber, polyurethane, and halogenating agent, and the mixture of rubber, polyurethane, and halogenating agent have strong adhesion to both polyolefin polymers and polar polymers. Therefore, the bonding surfaces of a laminate coated with an adhesive layer having such a composition are 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, 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 containing polar groups in the molecule such as IIR, CR, NER, IR, ACM, etc., or various synthetic resins containing polar groups in the molecule such as ABS resin, PS, PVC, nylon resin, etc. be. The laminate of the present invention is a molded product formed by laminating the above-mentioned polyolefin polymer and polar polymer, and is formed into a desired shape by various molding methods such as extrusion molding, injection molding, press molding, or vacuum forming. A shape is given. Next, the adhesive layer is composed of either (a) a mixture of rubber, polyurethane, and polyisocyanate, or (b) a mixture of rubber, polyurethane, and a halogenating agent. Here, rubber refers to the above-mentioned NR, SBR, BR, IIR,
Examples include natural and various synthetic rubbers such as CR, NER, IR, and ACM. In addition, these rubbers usually contain additives such as sulfur, morpholine disulfide, or dicumyl peroxide as vulcanizing agents, and 2-mercaptobenzothiazole, zinc dimethyldithiocarbamate, or tetramethyl as vulcanization accelerators. Thiuram disulfide, etc.
2,6-di-tert-butyl-p as an antioxidant
-cresol and 2,6-di-tert-butyl-4
- ethylphenol, etc., anti-aging agents such as phenyl-α-naphthylamine and N,N'-diphenyl-p-phenylenediamine, fillers such as carbon black, calcium carbonate, clay or hydrated silicic acid, and plasticizers such as dioctyl seba. Contains Kate, mineral oil, etc. Next, polyisocyanates are 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. 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.
It is a two-component curing type polyurethane containing groups or OH groups. The above polyol may be either a polyester polyol or a polyether polyol, and the polyol components of the polyester polyol 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 organic acid components 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. 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 preferable to use a polyester polyol that is not easily affected by this plasticizer. Furthermore, the various diisocyanates and polyfunctional isocyanates listed above may be used as the isocyanate. Next, the halogenating agent used in the present invention has in its molecule:

Typical examples include compounds containing [Formula] (wherein X represents halogen), alkyl hypohalides, or hypochlorites, but other chlorine, bromine, or aqueous solutions thereof; hypochlorites A mixture consisting of organic acid and
52216); Antimony pentafluoride (Special Publication 1972-
23483); Aqueous solution of alkali metal or alkaline earth metal; Mixed solution of sulfur fluoride and bromine (Japanese Patent Publication No. 57-27751); Mixture of iodine and potassium iodide (Japanese Patent Publication No. 53-27751); Halgen oxygen Mixed aqueous solution consisting of acid 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

[Example 1]

Unvulcanized rubber-1 was prepared by kneading a blend having the composition shown in Table-1.

[Table] In the same manner, unvulcanized rubbers 2 to 4 were prepared by kneading the compositions shown in Tables 2 to 4 below.

【table】

【table】

[Table] In addition, polyester polyol (or polyether polyol) and isocyanate were dissolved in a mixed solvent of 1,1,1-trichloroethane/dimethylformamide = 100/60 so that the solid content was 35%, and then dried. After reacting in nitrogen gas at 80°C for 3 hours, a chain extender was added and the reaction was further carried out at 80°C for 3 hours to prepare polyurethane. The composition and blending ratio (in terms of weight ratio) of the polyester polyol (or polyether polyol), isocyanate, and chain extender used are shown below. Polyurethane-1: Polypropylene glycol 164.0 parts (molecular weight = 2000) 4,4'-diphenylmethane diisocyanate
100.0 parts 1,6-hexanediol 24.8 parts Polyurethane-2: Polyethylene adipate 164.0 parts (molecular weight = 2000) Tolylene diisocyanate 69.6 parts 1,4-butanediol 18.9 parts Polyurethane-3: Polybutylene adipate 200.0 parts (molecular weight = 2000) Xylene diisocyanate 56.5 parts Ethylene glycol 11.8 parts Polyurethane-4: Polyethylene adipate 200.0 parts (molecular weight = 2000) Polypropylene glycol 100.0 parts (molecular weight = 1000) 4,4'-diphenylmethane diisocyanate
250.0 parts 1,6-hexanediol 89.8 parts Polyurethane-5: Polyethylene adipate 200.0 parts (molecular weight = 2000) 4,4'-diphenylmethane diisocyanate
100.0 parts 1,6-hexanediol 37.8 parts Polyurethane-6: Polyethylene adipate 100.0 parts (molecular weight = 1000) Hydrogenated 4,4-diphenylmethane diisocyanate 104.9 parts 1,5-pentanediol 32.3 parts Polyurethane-7: Polybutylene adipate 100.0 parts (molecular weight = 1000) Polypropylene glycol 400.0 parts (molecular weight = 2000) 4,4'-diphenylmethane diisocyanate
450.0 parts 1,6-hexanediol 180.8 parts A separately prepared polyisocyanate (or halogenating agent) is added to the polyurethane obtained as above and the unvulcanized rubber, and mixed in a solvent to form an adhesive. It was adjusted. The composition and blending ratio (in terms of weight ratio) of the unvulcanized rubber, polyurethane, and polyisocyanate (or halogenating agent) used are shown below. Adhesive 1: Only unvulcanized rubber-1 used Adhesive 2: Unvulcanized rubber-1 100.0 parts Polyurethane-4 4.0 parts N-bromsuccinimide 0.4 parts Adhesive 3: Unvulcanized rubber-1 100.0 parts Polyurethane-5 50.0 parts tertiary alkyl hypochloride 0.002 parts adhesive 4: Unvulcanized rubber-2 100.0 parts polyurethane-2 50.0 parts tertiary alkyl hypochloride 0.1 part adhesive 5: Unvulcanized rubber-3 100.0 parts polyurethane-2 50.0 parts Trichloroisocyanuric acid 0.05 parts Adhesive 6: Unvulcanized rubber-4 100.0 parts Polyurethane-2 50.0 parts Trichloroisocyanuric acid 0.05 parts Adhesive 7: Unvulcanized rubber-4 100.0 parts Polyurethane-2 50.0 parts Xylene diisocyanate 10.0 parts Adhesive 8: Unvulcanized rubber - 1 100.0 parts Polyurethane - 4 50.0 parts Hydrogenated 4,4'-diphenylmetal diisocyanate 0.1 part Adhesive 9: Unvulcanized rubber - 2 100.0 parts Polyurethane - 3 50.0 parts 4,4 '-diphenylmethane diisocyanate
10.0 parts adhesive 10: Unvulcanized rubber-1 100.0 parts polyurethane-6 50.0 parts Tris-(p-isocyanate phenyl)-thiophosphate 10.0 parts Adhesive 11: Unvulcanized rubber-4 100.0 parts polyurethane- 7 50.0 parts 4,4'-diphenylmethane diisocyanate
10.0 parts The solvents used were all 1, 1 and 1 above.
Trichloroethane/dimethyl formamide =
It is a 100/60 mixed solvent. Next, a resin plate was manufactured by extrusion molding a polypropylene resin, and the adhesive was applied to the surface of the resin plate, and then 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 a composition shown in Table 5 below were co-extruded to produce a plate-shaped laminate. Note that during this coextrusion molding, the rubber in the adhesive was vulcanized, and a curing reaction progressed to form an adhesive layer.

[Example 2]

The back side of the flocked cloth was lined with a sheet made of urethane resin that had been expanded 30 times. On the other hand, the adhesive 2 was applied to the surface of the polypropylene resin extrusion molded plate used in Example 1, and then hot air at 80° C. was blown onto the surface for 10 seconds to dry the coating to the touch. Further, this resin plate and the sheet made of the urethane resin described above were overlapped and press-molded at a pressure of 10 kg/cm ² to produce a plate-shaped laminate. Note that during this press molding, the rubber in the adhesive was vulcanized and a curing reaction progressed to form an adhesive layer. 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 a peel test was conducted to examine the adhesion of the bonded surfaces. In addition, laminates similar to those described above were manufactured using the adhesives 1 and 3 to 11, and the same peel test was conducted on these as well. As a result, all of the laminates showed good adhesion, except for the laminate using Adhesive 1 made of unvulcanized rubber 1 only. Next, after applying adhesives 1 to 11 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 11 on the surfaces thereof, the base material of the sheet is made of polyethylene resin foam. A plate-shaped laminate was manufactured by alternative press molding. Similar peel tests were conducted on these laminates, and as a result, all of them showed good adhesion, except for the laminate using Adhesive-1 made only of unvulcanized rubber-1. On the other hand, in the case of the laminates using each of the adhesives of Comparative Examples-1 to 9, the adhesion strength was weaker than that of the laminates using Adhesives-2 to 11. [Example 3] After applying adhesive 2 shown in Table 6 above to the surface of the polypropylene resin extrusion molded plate used in Example 1, hot air at 80°C was blown onto the surface for 10 seconds to form a coating film. was dry to the touch. Further, using this resin plate as an insert, vinyl chloride having the composition shown in Table 7 was injection molded to produce a plate-shaped laminate. Note that during this injection molding, the rubber in the adhesive was vulcanized and a curing reaction progressed to form an adhesive layer. 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 a peel test was conducted to examine the adhesion of the bonded surfaces. In addition, laminates similar to those described above were manufactured using Adhesives-1 and 3 to 11, and the same peel test was conducted on these as well. As a result, all of the laminates showed good adhesion, except for the laminate using Adhesive 1 made of unvulcanized rubber 1 only. On the other hand, in the case of the laminates using each of the adhesives of Comparative Examples-1 to 9, the adhesion strength was weaker than that of the laminates using Adhesives-2 to 11. [Example 4] After applying the adhesive 2 shown in Table 6 above to the surface of a 1.5 mm thick polypropylene resin sheet, the surface was
After drying the coating film to the touch by blowing hot air at 80°C for 10 seconds, a 1.5 mm thick polyamide resin sheet was bonded together and a laminated sheet was manufactured by vacuum forming. Note that the rubber in the adhesive was vulcanized by heating during vacuum forming, and a curing reaction progressed to form an adhesive layer. Next, this laminated sheet was left at room temperature for 7 days,
After leaving it in a constant temperature bath at 80°C for 1 hour, a peel test was conducted to examine the adhesion of the bonded surfaces. In addition, laminated sheets similar to those described above were manufactured using the adhesives 1 and 3 to 11, and the same peel test was conducted on these as well. As a result, all of the sheets exhibited good adhesion, except for the case of the laminated sheet using Adhesive-1 consisting only of unvulcanized rubber-1. On the other hand, in the case of the laminated sheets using each of the adhesives of Comparative Examples-1 to 9, the adhesion strength was weaker than that of the adhesives using Adhesives-2 to 11. In this way, in a molded article in which various polyolefin polymers and a polar polymer are laminated, an adhesive-2 to 11
By coating and forming an adhesive layer consisting of the following, it is possible to obtain a laminate in which the bonding surfaces are firmly adhered for a long period of time. Effects of the Invention As detailed above, an adhesive layer made of a mixture of the rubber, polyurethane, and polyisocyanate, or a mixture of rubber, polyurethane, and halogenated A laminate formed by coating an adhesive layer made of a mixture with a bonding agent exhibits an excellent effect in that the bonding surfaces thereof are firmly adhered for a long period of time. Therefore, the laminate of the present invention can be applied to various laminates composed of a polyolefin polymer and a polar polymer, such as automotive weather strips, glass runs, flocked products, or moldings with a resin tape attached to the back side. This is an excellent invention that can be transformed into

Claims (1)

[Scope of Claims] 1. In a molded article formed by laminating a polyolefin polymer and a polar polymer, the joining surface of the two polymers includes (a) an adhesive layer made of a mixture of rubber, polyurethane, and polyisocyanate; or (b) a laminate formed by coating an adhesive layer consisting of a mixture of rubber, polyurethane, and a halogenating agent. 2. Claim 1, wherein the adhesive layer is a mixture of 4 to 300 parts by weight of polyurethane and 0.1 to 50 parts by weight of polyisocyanate to 100 parts by weight of rubber. The described laminate. 3 The adhesive layer contains 4 to 300 parts by weight of polyurethane and 0.002 parts by weight of halogenating agent per 100 parts by weight of rubber.
2. The laminate according to claim 1, wherein the laminate is mixed in a proportion of 20 parts by weight. 4. The laminate according to claim 1, wherein the polyurethane is a polyester polyurethane containing an NCO group or an OH group at the molecular terminal. 5. 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, and (c) a hypohalite. The laminate according to claim 1, characterized in that the laminate is made of at least one of: