Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/04—Homopolymers or copolymers of ethene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/29—Laminated material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2475/00—Presence of polyurethane

Definitions

• the present invention relates to an adhesive composition, an adhesive laminate, a method for producing a multilayer laminate, and a multilayer laminate. More specifically, the present invention can laminate a thermoplastic elastomer composition layer and a polyurethane layer with sufficient adhesive force, does not require a complicated process, and furthermore, eliminates a solvent having a problem in working environment and general environment.
• the present invention relates to an adhesive composition, an adhesive laminate, a method for producing an adhesive laminate, and a multilayer laminate which do not require the use of an adhesive (primer) contained therein.
• Laminates comprising a thermoplastic elastomer composition as a skin layer and having the skin layer and a polyurethane layer are widely used in various fields, such as automotive interior parts.
• a thermoplastic elastomer composition layer and a polyurethane layer they are inferior in adhesion when both layers are bonded by a heat fusion method.
• a method for improving the adhesiveness a method using an adhesive (primer) is known.
• the adhesive has to be applied after cooling once, which causes a problem that the process becomes complicated.
• the adhesive usually contains a solvent, but there is a problem in that the solvent is volatilized in the coating-drying process, thereby contaminating the working environment.
• thermoplastic elastomer-composition layer and the polyurethane layer can be laminated with a sufficient adhesive force, and a complicated process is not required in the adhesion.
• An adhesive composition, an adhesive laminate, a method for producing an adhesive laminate, and a multilayer laminate which do not require the use of an adhesive (primer) containing a solvent. Disclosure of the invention
• the present invention relates to an ethylene-based polymer powder and an adhesive composition obtained by dry-blending 0.1 to 10 parts by weight of an organic peroxide with respect to 100 parts by weight of the powder;
• the adhesive laminate of the first invention is supplied to the surface of the thermoplastic elastomer composition layer and the adhesive laminate comprising the layer composed of the composite and the thermoplastic elastomer composition layer, and is heat-sealed.
• the present invention relates to a method for producing the adhesive laminate, and a multilayer laminate obtained by laminating a thermoplastic elastomer composition layer and a polyurethane layer via a layer comprising the adhesive composition.
• the ethylene polymer powder used in the present invention is a thermoplastic resin containing ethylene as a main component, such as a high-pressure polyethylene, a low-pressure polyethylene, a chain low-density polyethylene, and an ethylene-vinyl acetate copolymer.
• ethylene-vinyl acetate copolymer such as a high-pressure polyethylene, a low-pressure polyethylene, a chain low-density polyethylene, and an ethylene-vinyl acetate copolymer.
• Ethylene-methacrylic acid copolymer ethylene-acrylic acid ester-maleic anhydride terpolymer
• ethylene-glycidyl methacrylate copolymer ethylene-glycidyl methacrylate
• the powder of the ethylene polymer preferably has an average particle size of 50 to 1200 m. If the average particle size is too small, the fluidity of the powder may be poor, while if the average particle size is too large, the feel of the molded article may be reduced.
• organic peroxide used in the present invention examples include ketone peroxides (eg, ethyl methyl ketone peroxide), peroxyketals (1,1,1-bis (tert-butyl peroxy) 13,3,5- Trimethylcyclohexane, etc.), Hide mouth peroxyde (Tertiary butyl hydroperoxide, etc.), Dialkyl peroxyside (Yuichi Shary butyl peroxyde, etc.), Diacyl peroxyside (Benzoyl peroxyside) ), Peroxyesters (e.g., slivers, benzyl chloride, etc.), peroxydicarbonates (di (2-ethylhexyl) C) peroxydicarbonate, etc.).
• ketone peroxides eg, ethyl methyl ketone peroxide
• peroxyketals 1,1,1-bis (tert-butyl peroxy) 13,3,5- Trimethylcyclohexane, etc
• the adhesive composition of the present invention comprises 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight of an organic peroxide based on 100 parts by weight of the ethylene polymer powder and the powder. It can be obtained by driving the part. If the amount of the organic peroxide is too small, the adhesion to the polyurethane layer will be poor. On the other hand, if the amount of the organic peroxide is too large, the cost of the adhesive composition will increase.
• Examples of the method of dry blending the ethylene polymer powder and the organic peroxide include a method of mixing the ethylene polymer powder and the organic peroxide at a temperature lower than the melting temperature of the ethylene polymer, Generally, a mixer such as a fixed container mixer such as a rotating container mixer or a super mixer is used.
• the adhesive composition of the present invention contains the above-mentioned ethylene polymer powder and an organic peroxide.
• bismaleimide or triallyl isocyanate may be used, if necessary.
• Crosslinking aids such as nurate, pigments and the like may also be included.
• the adhesive laminate of the present invention is an adhesive laminate comprising the above-mentioned layer of the adhesive composition and a layer of a thermoplastic elastomer composition.
• a polyolefin-based resin is a polymer or copolymer of one or more types of olefins having crystallinity.
• the olefin preferably ethylene, propylene, olefin having 2 to 8 carbon atoms such as 1-butene, etc.
• polyethylene, polypropylene, a copolymer of propylene and ethylene an example is a copolymer of propylene and a non-propylene olefin such as 1-butene.
• the rubbery polymer examples include a conjugated gen-based polymer rubber or a hydrogenated product thereof, and an ethylene-vinyl olefin copolymer rubber, and the like. These rubbery polymers are thermoplastic elastomer compositions. Singly or in plural.
• Conjugated gen-based polymer rubber is one type of conjugated polymer or two or more types of conjugated A polymer rubber obtained by copolymerization of conjugated gen and a copolymer of conjugated gen and a monomer other than conjugated gen.
• conjugated gen include butadiene, isoprene, 1,3-pentene And conjugated diene having 4 to 8 carbon atoms such as 2,2,3-dimethylbutadiene.
• Monomers other than the conjugated diene include, for example, vinyl aromatic compounds (eg, styrene, monomethylstyrene, p, m, or 0-methylstyrene), vinyl ester compounds (eg, vinyl acetate), ethylenically unsaturated Examples thereof include carboxylate esters (for example, methyl acrylate, methyl methacrylate, glycidyl methacrylate and the like), vinyl nitrile compounds (for example, acrylonitrile and methacrylonitrile).
• vinyl aromatic compounds eg, styrene, monomethylstyrene, p, m, or 0-methylstyrene
• vinyl ester compounds eg, vinyl acetate
• ethylenically unsaturated examples thereof include carboxylate esters (for example, methyl acrylate, methyl methacrylate, glycidyl methacrylate and the like), vinyl nitrile compounds (for example, acryl
• the ethylene monoolefin copolymer rubber is preferably a copolymer of ethylene and propylene, 3-olefin, 1-butene, 1-hexene or 1-octene having 3 to 10 carbon atoms, It is a copolymer of ethylene, the one-year-old olefin and a non-conjugated gen, and has almost no crystallinity.
• the adhesive laminate can be obtained by supplying the adhesive composition to the surface of the thermoplastic elastomer composition layer and performing heat fusion. More specifically, the thermoplastic elastomer composition is powder-formed. Thus, a thermoplastic elastomer composition layer is obtained, and then an adhesive composition is supplied to the surface of the thermoplastic elastomer composition layer and heat-sealed.
• the surface temperature of the thermoplastic elastomer composition layer when the adhesive composition is supplied to the surface of the thermoplastic elastomer composition layer is preferably equal to or higher than the melting point of the adhesive composition.
• the adhesive laminate is preferably produced by powder molding, since a complicated pattern such as embossing or stitching can be easily formed on the surface of the thermoplastic elastomer composition layer.
• the powder molding include, for example, heating a powder of the thermoplastic elastomer composition to a temperature sufficiently higher than the melting temperature of the composition, and a mold for powder molding which may have a complicated pattern on its surface. And heat-fusing the powders together into a sheet on the mold surface, and removing the unfused powder to form a thermoplastic elastomer composition layer.
• the adhesive composition is applied on the thermoplastic elastomer composition layer. And the powders are heat-fused to obtain an adhesive laminate comprising a thermoplastic elastomer composition layer and an adhesive composition layer.
• the multilayer laminate of the present invention is a multilayer laminate obtained by laminating a thermoplastic elastomer composition layer and a polyurethane layer via a layer composed of the adhesive composition, or a polyurethane of the multilayer laminate. It is a multilayer laminate obtained by laminating a thermoplastic resin reinforcement outside the layer.
• a pair of male and female molds for molding a polyurethane layer, and the above-mentioned adhesive laminate and a thermoplastic resin reinforcing layer molded by injection molding or the like are set.
• a polyurethane layer is formed by injecting, foaming, and hardening a mixture of the resin and the polyol to obtain a multilayer laminate comprising an adhesive laminate, a polyurethane layer, and a thermoplastic resin reinforcing layer.
• the multilayer laminate of the present invention is suitable for interior parts such as instrument panels, door trims, console boxes and console boxes, and exterior parts such as spoilers, side moldings and mirror housings in the field of automobiles.
• interior parts such as instrument panels, door trims, console boxes and console boxes
• exterior parts such as spoilers, side moldings and mirror housings in the field of automobiles.
• exterior members such as spoilers, side moldings and mirror housings in the field of automobiles.
• it is suitable as an exterior member for TVs, videos, washing machines, coolers, air conditioners, and the like.
• MFR Melt edge ratio
• ethylene-propylene random copolymer containing 5% by weight of ethylene and styrene 40% by weight of butadiene-styrene copolymer rubber of 10% by weight
• hydrogenation rate 99%
• MFR 10 g / 10min, load 2.16kg, 230 ° C
• propylene content 27mo 1%
• 20 parts by weight of ethylene-propylene copolymer rubber having 1 ⁇ 1 of 1 (g / 10 minutes, load 2.16 kg, 190 ° C) was kneaded using a twin-screw extruder to obtain a pellet.
• the pellet is liquid nitrogen
• the powder was mechanically pulverized in an atmosphere cooled to 0 ° C to obtain a powder of a thermoplastic elastomer composition layer having an average particle size of 19.
• Pellets of ethylene-glycidyl methacrylate vinyl acetate terpolymer (MFR 20 g / 10 min, load 2.16 kg, 190 ° C) with glycidyl methacrylate content of 12% by weight and vinyl acetate content of 5% by weight Is mechanically pulverized in an atmosphere cooled to 80 ° C with liquid nitrogen (average particle size: 22 O jLLm) 50 parts by weight, glycidyl methacrylate content 18% by weight, vinyl acetate content 1 Weight percent ethylene-glycidyl methacrylate biacetate monoacetate terpolymer (MFR 340 g / 10 min, load 2.16 kg 190 ° C) pellets in liquid nitrogen in an atmosphere cooled to 80 ° C Mechanically ground powder (average particle size 13 O jum) 50 parts by weight and organic peroxide YP-63S, 3 parts by weight, manufactured by Kayaku Axo Co., Ltd., Nippon Kasei Co., Ltd
• the adhesive laminate was set in a polyurethane layer molding die, a mixed solution of polyol and isocyanate was supplied to the adhesive layer side of the adhesive laminate, and the mold was clamped, followed by foaming and curing to obtain a multilayer laminate.
• Table 1 shows the results of the adhesion test between the adhesive laminate and polyurethane.
• thermoplastic elastomer composition layer obtained in Reference Example was sprinkled on a nickel electroplated plate heated to 260 ° C, and after 7 seconds, the unmelted and unadhered powder was wiped off. Was. Further, the mold was placed in an oven heated to 260 ° C. for 60 seconds and heated. After 60 seconds, the sheet was taken out of the oven, cooled, and demolded, to obtain a sheet made of a thermoplastic elastomer composition.
• the sheet made of the thermoplastic elastomer composition was set in a mold for a polyurethane layer, a mixed solution of a polyol and an isocyanate was supplied, and the mold was clamped, followed by foaming and curing to obtain a multilayer laminate. Table 1 shows the results of the adhesion test between the thermoplastic elastomer composition sheet and the polyurethane. Table 1
• thermoplastic elastomer composition layer and a polyurethane layer with sufficient adhesive force, and does not require a complicated process, and furthermore, includes a solvent containing a solvent having a problem in working environment.
• ADVANTAGE OF THE INVENTION The adhesive composition which does not use an agent (primer), an adhesive laminated body, the manufacturing method of an adhesive laminated body, and a multilayer laminated body can be provided.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Lining Or Joining Of Plastics Or The Like (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=13428322

Family Applications (1)

Country Status (5)

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Citations (3)

• 1998
  • 1998-03-19 JP JP7033098A patent/JP4085187B2/ja not_active Expired - Fee Related
• 1999
  • 1999-03-16 KR KR1020007010205A patent/KR20010041901A/ko not_active Application Discontinuation
  • 1999-03-16 DE DE1999183050 patent/DE19983050T1/de not_active Withdrawn
  • 1999-03-16 WO PCT/JP1999/001276 patent/WO1999047622A1/ja not_active Application Discontinuation
  • 1999-03-16 CN CN99804163A patent/CN1293704A/zh active Pending

Patent Citations (3)

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