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WO1992012008A1 - Feuilles multicouches ayant un excellent pouvoir adhesif - Google Patents

Feuilles multicouches ayant un excellent pouvoir adhesif Download PDF

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Publication number
WO1992012008A1
WO1992012008A1 PCT/US1991/009511 US9109511W WO9212008A1 WO 1992012008 A1 WO1992012008 A1 WO 1992012008A1 US 9109511 W US9109511 W US 9109511W WO 9212008 A1 WO9212008 A1 WO 9212008A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet material
ethylene
layer
material according
copolymer
Prior art date
Application number
PCT/US1991/009511
Other languages
English (en)
Inventor
Richard Van Brooks
Edward Rudolph Hollander, Jr.
Michael Charles Carmody
Original Assignee
Eastman Kodak Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Publication of WO1992012008A1 publication Critical patent/WO1992012008A1/fr

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Classifications

    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2377/00—Polyamides
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • This invention relates to multilayered films or sheets which have excellent adhesion. More particularly, the invention relates to multilayered sheets wherein a tie layer of a particular polyethylene is used to bond a layer of thermoplastic nylon or a nylon blend with a layer of a thermoplastic polyester or polyolefin. Because of the sheet having excellent adhesion, both between layers and to other substrates, it is especially useful as a carrier for decorative and protective coatings to be applied to substrates such as automobile panels.
  • sheet(s) or “sheet material” includes thin film material as well as heavier sheets. Patents of interest include U.S. Patents
  • the '926 patent discloses a flexible film comprising several layers of polymeric material.
  • one of the flexible films disclosed comprises a polyaHomer and a flexible copolyester tied together with various tie layers (for example, an ethylene propylene copolymer. Column 4, lines 7 and 8).
  • Applicants' invention obtains unexpected improved results in adhesion using the low molecular weight polyethylene having a flow rate of 0.25 to 40 over the tie layers disclosed by this patent.
  • published technical literature by Mitsui Petrochemical Industries, Ltd., directed to Admer resins discloses the utility of low molecular weight polyethylene resins as adhesive layers between various materials including certain plastics.
  • multilayered films having excellent adhesion.
  • the films are normally coextruded into three or five layered structures, i.e.. A—B—C or A—B—C—B-A, wherein A is a thermoplastic polyamide or polyamide blend, B is a modified low molecular weight polyethylene resin as defined herein, and C is a polyester or polyolefin.
  • sheet material adapted for in—mold injection molding applications comprising a first outer layer, an intermediate tie layer and a second outer layer, a) the first outer layer comprising a crystalline or amorphous thermoplastic polyamide, b) the tie layer comprising a copolymer of ethylene or propylene and at least one other unsaturated monomer, the copolymer having a density of 0.85—1.00 g/cc, and c) the second outer layer comprising a polyolefin or polyester, the polyolefin being selected from polyethylene, polypropylene and ethylena/ ropylene copolymers having a melt flow rate of 4 to 20, and the polyester being selected from polymers and copolymers of polyethylene terephthalate, polycyclohexylene— dimethylene terephthalate, polybutylene terephthalate, and blends and copolymers thereof.
  • the sheets as described above are particularly useful for in—mold applications when polyolefin and a second
  • Typical polyamides include polycaprolactam (Nylon 6) , poly— ⁇ -aminoheptanoic acid (Nylon 7) , poly—o-j—aminonomanoic acid (Nylon 9) , polyundecanamide (Nylon 11) , polylauryllactam (Nylon 12) , polyethylene adipamide (Nylon 2—6) , polytetramethylene adipamide (Nylon 4-6) , poly—hexamethylene adipamide (Nylon 6-6) , polyhexamethylene sebacamide (Nylon 6—10) , polyoctamethylene adipamide (Nylon 8—6) , polydecamethylene adipamide (Nylon 10—6) and polydodecamethylene sebacamide (Nylon 12-10) .
  • Polyamides prepared from aromatic amino compounds are disclosed in U.S. Patent No. 3,408,334.
  • the aromatic amines used in these polyamides contain amino groups bonded directly to an aromatic ring.
  • suitable diamines are metaphenylenediamine, para—phenylenediamine, isomeric diaminoxylenes, etc.
  • the patent further discloses that p— henylene— dioxydiacetic acid and similar compounds can be employed in the preparation of polyamides.
  • U.S. Patent No. 4,482,695 discloses polyamides prepared from an aliphatic diamine and a dicarboxylic acid which is a diacetic acid.
  • the polyamide or polyamide blend which is employed in the present invention exhibits an inherent viscosity of 0.4 to 1.5.
  • the inherent viscosity is measured at 25°C in a 60/40 by weight mixture of phenol./ tetrachloroethane at a concentration of 0.5 g/100 ml.
  • Polymers having an inherent viscosity within this range are of sufficiently high molecular weight to be used in the present invention.
  • polyamides used in the present invention are synthesized by methods generally known in the art for 4 -
  • the diamine and diacid components are preferably reacted in approximately stoichiometic quantities.
  • Diacid chlorides, esters, and the like can be used.
  • a solvent may be used in the preparation of 5 the polyamide.
  • the reaction involves heating approximately stoichiometric quantities of the diamine and diacid components in the presence of a small amount of water and in an inert atmosphere, such as nitrogen, 10 with stirring. A slight excess of the diamine may be desirable. Water is allowed to distill as the temperature is raised so as to facilitate reaction between the diamine and the dicarboxylic acid. Temperatures in the range of about 180° to 330°C may be 15 employed, with the preferred range being about 200° to
  • the final stages of the reaction are conducted under a vacuum.
  • the polymerization reaction is typically conducted for a period of time of about 2 to 30 hours.
  • the preparation of the polyamide does not 20 require the use of a catalyst, and catalysts typically are not employed during the reaction period.
  • suitable catalysts which have been disclosed in the literature can be employed if desired.
  • Blends of the nylon described above may also be 25 used for the outer layer A.
  • Typical polymers which may be blended with the nylon are polyesters and styrenic copolymers.
  • the term "nylon” as used herein is intended to include blends of nylon with up to about 50 weight % of such polymers. 30
  • the term “polyester” as used herein is intended to include copolyesters. Conventional polyesters, made using well—known conventional techniques, may be used for the layer C.
  • the polyester may be made having repeat units from the glycols and dicarboxylic acids identified below.
  • the glycol component of the polyester may include aliphatic or alicyclic glycols.
  • these glycols include ethylene glycol; propylene glycol;
  • 1,3-propanediol 2—ethyl-2—isobutyl-1,3-propanediol; 1,3—butanediol, 1,4—butanediol; neopentyl glycol;
  • 1,2 cyclohexanedimethanol
  • 1,3 cyclohexanedimethanol
  • Copolymers may be prepared from two or more of the above glycols.
  • the dicarboxylic acid component of the polyester comprises aliphatic dicarboxylic acid, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids.
  • dicarboxylic acids include succinic; glutaric; adipic; azelaic; sebacic; fumaric; aleic; itaconic;
  • 1,4 cyclohexanedicarboxylic; phthalic; terephthalic, isophthalic, and naphthalene dicarboxylic acid. It should be understood that use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid”.
  • the outer layer C may be a polyester as described above, or it may be a polyolefin.
  • Polymers or copolymers of a—olefins having 2 to 6 carbon atoms may be used. Preferred are polyethylene or polypropylene. Suitable polyolefins are commercially available, and include such materials as Tenite (trademark) polypropylene—4240 (melt flow rate of 9.0 g./10 min) and Tenite (trademark) polyallomer—5L2S (melt flow rate of 6.0 g/10 min) , both available from Eastman Chemical Products, Inc. and Shell polypropylene WRS7—327 (melt flow rate of 8 g/10 min) . Polyolefins used have a melt flow rate of 4—20, preferably 5—12.
  • the tie layer used in this invention is described as a low molecular weight copolymer of ethylene or propylene having as melt flow rate of 0.25 to 40.0 g/10 min., a tensile strength at break of at least 25 kg/cm , an elongation at break of greater than 50%, a melting point of at least 65°C and a density of 0.85—1.00 g/cc) .
  • the tie layer material of this invention is further described as having 0.1 to 30 weight percent of at least one unsaturated monomer copolymerized with ethylene, e.g., maleic acid, fumaric acid, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, methacrylonitrile, butadiene, carbon monoxide, etc.
  • ethylene e.g., maleic acid, fumaric acid, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, methacrylonitrile, butadiene, carbon monoxide, etc.
  • acrylic esters, maleic anhydride, vinyl acetate, and methacrylic acid are commercially available under trademarks such as Admer AT-469C, Lotader AX-8040, Elvax 260, Dupont CXA3036 and 3101 and Lotader HX-8020.
  • the thicknesses of the layers are about 4—20 mils for the polyurethane elastomer, 0.5—3.0 mils for the tie layer and 4—20 mils for the amorphous copolyester.
  • the films according to the present invention are preferably formed by cast coextrusion using conventional techniques.
  • the sheet material of this invention preferably includes a protective and decorative layer such as a paint layer on one of the outer layers.
  • the preferred manner of using the sheet material of this invention comprises the steps of providing a mold in the configuration of the shaped article; positioning within the mold the above described multilayered sheet material, injecting into the mold a fluid composition which is capable of hardening to both form the desired shaped article and bond to the sheet material; and removing from the mold a shaped article having a protective and decorative coating formed from the sheet material securely bonded thereto.
  • the sheet material is placed in a mold cavity, and a molding material is injected into the mold cavity under pressure against the sheet material such that the sheet material conforms to the shape of the molded article and bonds to the outer surface of the article.
  • the molding material is to be polyolefin
  • the layer C should be polyolefin
  • the layer C should be polyester.
  • Suitable molds, molding compositions and molding process parameters for this method are well known and form no part of the present invention.
  • the sheet material may be preshaped prior to being placed in the mold.
  • conventional thermoforming techniques may be used.
  • the film layer materials may also contain stabilizers, colorants, processing aids, glass fibers, and flame retardants.
  • This in—mold application of film laminates would preferably be applied to injection— olded parts which could be used in a number of applications. .An example would be automobile or truck parts such as bumpers, fascia, and trim applications (flexible or rigid) such as claddings, trim strips. These applications would be useful for parts experiencing high wear forces or loadings such as parts for materials handling equipment, recreational equipment or vehicles.
  • the film laminate could also be used with reaction injection molding processes and with vacuum forming processes.
  • tie layers are described as follows:
  • Copolymer having following properties: -3 8 E-319
  • a three—layer film laminate is coextruded from Allied Chemical Capron 8200 HS nylon 6 for the outside layer (layer A) , Mitsui ADMER AT469C modified polyolefin for the tie layer (layer B) , and Shell polypropylene WRS7—327 for the layer C.
  • the melt temperatures are 255, 268, and 268°C for layers A, B and C, respectively.
  • Coextrusion block temperatures are set at 263°C.
  • Film thicknesses are 5.0, 2.0, and 3 mils, for layers A, B and C, respectively. Coextruded film is placed in the mold of an injection molding machine.
  • Thermoplastic polyolefin is injection molded onto the film with a melt temperature of 442°F (228°C) and mold temperature of 98-104°F (37-40 ⁇ C).
  • This TPO contains Shell WRS7-328 polypropylene. Thickness of the TPO substrate for this process is about .10 in.
  • Peel strength of the three layer film laminate is measured using a 180 degree peel test (ASTM D903) at a peel rate of 2 in./min (5.08 cm in) . After the TPO is injection molded onto the film, the average peel strength is measured to be 10.9 lb/in. (194 g/mm) , and maximum peel strength was 11.6 lb/in. (207 g/mm).
  • ASTM D903 180 degree peel test
  • the same film components for layers A and C as for Example 1 are used.
  • the tie layer B is Dupont Bynel E306.
  • the melt temperatures are 265, 250, and 240°C for layers A, B and C, respectively.
  • Coextrusion block temperature is 265°C.
  • Film thicknesses are 4.5, 2, and 4 mils for layers A, B and C, respectively.
  • Injection molding conditions are the same as those used in Example 1. After injection molding of the TPO onto the film, average peel strength for the coextruded film is 10.8 lb/in. (193 g/mm) and peak strength is 11.1 lb/in. (198 g/ ⁇ am) .
  • Example 3 A three—layer film laminate is coextruded from GE Noryl N-300 polyphenylene oxide/nylon blend for outside layer A, Mitsui .ADMER AT469C modified polyethylene for the tie layer (layer B) , and Shell polypropylene WRS7—327 for layer C.
  • the melt temperatures are 275, 260, and 239°C for layers A, B and C, respectively.
  • Coextrusion block temperature is set at 310°C.
  • Film thicknesses are 5.0, 2.0, and 3 mils, for layers A, B and C, respectively. Peak peel strength is measured to be 4.1 lb/in. (73 g/mm) and the average peel strength is 3.1 lb/in. (55 g/mm).
  • Thermoplastic polyolefin described in Example 1 is injection molded onto the film with a melt temperature of 442°F (228°C) and mold temperature of 98—104 ⁇ F (37—40 ⁇ C) . After molding the peak peel strength is 3.7 lb/in. (66 g/mm) and the average peel strength is 3.1 lb/in. (55 g/mm) .
  • a three—layer film laminate is coextruded with the same layer A and C materials as in Example 3.
  • the tie layer B is changed to Shell Kraton G—1901X elastomer.
  • Extrusion temperatures and layer thicknesses are the same as for Example 3.
  • Thermoplastic polyolefin as described in Example 1 is injection molded onto the film with a melt temperature of 442°F (228°C) and mold temperature of 98—104°F (37-40°C) . After molding, the peak peel strength is measured to be 13.9 lb/in. (248 g/mm) and the average peel strength 11.2 lb/in. (200 g/mm) .
  • a three—layer film laminate is coextruded from Monsanto Triax 1120 nylon/acrylonitrile—butadiene— styrene blend for outside layer A, Mitsui ADMER AT469C modified polyethylene for the tie layer B, and Shell polypropylene WRS7—327 for the inside layer C.
  • the melt temperatures are 274, 254, and 225°C for layers A, B and C, respectively.
  • Coextrusion block temperature is set at 270°C.
  • Film thicknesses are 5.0, 2.5, and 3 mils, for layers A, B and C, respectively. Peak peel strength for the coextruded film before injection molding is 2.7 lb/in. (48 g/mm) and average peel strength is 2.1 lb/in.
  • Thermoplastic polyolefin as described in Example 1 is injection molded onto the film with a melt temperature of 442°F (228°C) and mold temperature of 98—104°F (37—40°C). After molding the peak peel strength is 4.3 lb/in. (77 g/mm) and the average peel strength is 3.2 lb/in. (57 g/mm).
  • Example 6 A three—layer film laminate is coextruded with the same materials as in Example 5 except that the tie layer is Dupont Bynel E359. Extrusion temperatures and film thicknesses are the same as for Example 5. Peak peel strength is .9 lb/in. (16 g/mm) and average peel strength is .6 lb/in. (11 g/mm) for the film laminate before injection molding. Thermoplastic polyolefin as described in Example 1 is injection molded onto the film with a melt temperature of 442°F (228°C) and mold temperature of 98—104°F (37—40°C) . This TPO contains Shell WRS7-328 polypropylene. Thickness of the TPO substrate for this process is about .10 in. After molding the peak peel strength is 2.8 lb/in. (50 g/mm) and the average peel strength is 2.4 lb/in. (43 g/mm).
  • a three—layer film laminate is coextruded from the copolyester poly(cyclohexylenedimethylene terephthalate) for the outside layer C, Mitsui ADMER AT469C modified polyethylene for the tie layer B, and Allied Chemical Capron 8200 HS nylon 6 for the layer A.
  • the melt temperatures are 289, 271, and 260°C for layers C, B and A, respectively.
  • Coextrusion block temperature are set at 298°C.
  • Film thicknesses are 5.0, 2.0, and 3 mils, for layers C, B and A, respectively.
  • Nylon 6 (same material as for layer A of the film laminate) is injection molded onto the film with a melt temperature of 450°F (232°C) and mold temperature of 98-104°F (37—40 ⁇ C) . Thickness of the nylon substrate for this process is about .10 in.
  • Peel strength of the three layer film laminate is measured using a 180 degree peel test (ASTM D903) at a peel rate of 2 in./min (5.08 cmmin) . The average peel strength is measured to be 7.3 lb/in. (130 g/mm) and peak peel strength to be 7.5 lb/in. (134 g/aim) . After the nylon is injection molded onto the film, the average peel strength is measured to be 8.2 lb/in. (147 g/mm) and peek peel strength to be 10.3 lb/in. (184 g mm).
  • Example 7 Processing conditions are identical to those for Example 7 except that the tie layer material is DuPont Bynel CXA 3101. Average peel strength of the film laminate is 5.8 lb/in. (104 g/mm) and peak peel strength is 10.6 lb/in. (189 g/mm). After molding the average peel strength is 8.6 lb/in. (154 g/mm) and the peak peel strength is 10.8 lb/in. (193 g/mm).
  • the tie layer material is DuPont Bynel CXA 3101.
  • Average peel strength of the film laminate is 5.8 lb/in. (104 g/mm) and peak peel strength is 10.6 lb/in. (189 g/mm). After molding the average peel strength is 8.6 lb/in. (154 g/mm) and the peak peel strength is 10.8 lb/in. (193 g/mm).
  • a three—layer film laminate is coextruded from copolyester polycarbonate blend for the outside layer C, Shell Kraton G—2720X for the tie layer B, and Allied Chemical Capron 8200 HS nylon 6 for the layer A.
  • the copolyester contains repeat units from terephthalic acid about 75—85 ol % 1,4—cyclohexanedimethanol and about 25—15 mol % ethylene glycol.
  • the melt temperatures are 268, 260, and 262°C for layers C, B and A, respectively.
  • Coextrusion block temperature is set at 278°C.
  • Film thicknesses are 4.0, 2.0, and 3.5 mils, for layers C, B and A, respectively.
  • Average peel strength for the film laminate is measured to be 4.2 lb/in. (75 g/mm) and the peak peel strength is 4.4 lb/in. (79 g/mm) .
  • Nylon 6 similar to the layer A material is injection molded onto the film with a melt temperature of 450°F (232°C) and mold temperature of 98—104°F (37—40°C) . After molding the average peel strength is 3.8 lb/in. (66 g/mm) and peak peel strength is 5.2 lb/in. (93 g.mm) .
  • a three—layer film laminate is coextruded from Allied Chemical Capron 8200 HS nylon 6 the outside layer A, DuPont Bynel CXA 3101 for the tie layer B, and polyethylene terephthalate (PET) for the layer C.
  • the melt temperatures are 272, 250, and 244°C for layers A, B and C, respectively.
  • Coextrusion block temperature is set at 275°C.
  • Film thicknesses are 5.0, 2.5, and 3 mils, for layers A—C.
  • Average peel strength for the coextruded film before injection molding is 3.2 lb/in. (57 g/mm) and peak peel strength is 4.5 lb/in.
  • Glass—fiber reinforced PET is injection molded onto the film with a melt temperature of 520°F (27l°C) and mold temperature of 98-l04°F (37-40°C) .
  • a smooth film-molded sample laminate is formed with average peel strength of 3.2 lb/in. (57 g/mm) and the peak peel strength of 3.8 lb/in. (68 g/mm).
  • a three—layer film laminate is coextruded from Allied Chemical Capron 8200 HS nylon 6 the outside layer A, DuPont Bynel CXA E319 for the tie layer (layer B) , and polyethylene terephthalate for layer C. Processing conditions are the same as for Example 10. Average peel strength for the coextruded film before injection molding is 2.5 lb/in. (45 g/mm) and peak peel strength is 4.8 lb/in. (86 g/mm). Glass—fiber reinforced PET is injection molded onto the film with a melt temperature of 520°F (271°C) and mold temperature of 98-104°F (37-40°C). A smooth film-molded sample laminate is formed with average peel strength of
  • adhesion between this sheet and the substrate.
  • using the protective and decorative sheet according to this invention provides a high quality coating of attractive appearance. There appear to be no detrimental effects on the finish resulting from the molding procedure.
  • inherent viscosity I.V.
  • the "melting point" (T ) of the polymers described in this application are readily obtained with a Differential Scanning Calorimeter.
  • the strength of the bonds is determined by the "Peel Test” based on a modification (i.e., three test specimens) of the ASTM “T—Peel Test” set forth on pages 63 and 64 of the 1964 edition of the BOOK OF ASTM STANDARDS, published by the American Society of Testing Materials, and more specifically identified as Test Number D-1876-61-T.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention se rapporte à des feuilles multicouches, formées de préférence par co-extrusion, qui comprennent une couche externe d'un nylon ou d'un mélange de nylon thermoplastique, une couche externe de polyester ou de polyoléfine, ainsi qu'une couche d'attache à base d'un polypropylène ou d'un polyéthylène modifié. Ces feuilles possèdent un excellent pouvoir adhésif et sont utilisables notamment comme support pour revêtements décoratifs et/ou protecteurs.
PCT/US1991/009511 1991-01-02 1991-12-18 Feuilles multicouches ayant un excellent pouvoir adhesif WO1992012008A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US63680591A 1991-01-02 1991-01-02
US636,805 1991-01-02

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WO1992012008A1 true WO1992012008A1 (fr) 1992-07-23

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PCT/US1991/009511 WO1992012008A1 (fr) 1991-01-02 1991-12-18 Feuilles multicouches ayant un excellent pouvoir adhesif

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0694377A3 (fr) * 1994-07-29 1996-06-05 Graziola Spa Procédé et apparail pour la réalisation d'une représentation graphique sur un objet en polyoléfine et film utilisé dans ce procédé
JP2000153536A (ja) * 1998-11-24 2000-06-06 Nissha Printing Co Ltd インサートフィルム
FR2804364A1 (fr) * 2000-02-02 2001-08-03 Plastic Omnium Cie Procede de fabrication d'une piece en matiere plastique comportant un film decoratif, et piece ainsi obtenue
EP0995571A4 (fr) * 1998-02-27 2003-01-29 Nissha Printing Feuille pour decoration dans le moule et article decore dans le moule
WO2006087250A1 (fr) * 2005-02-19 2006-08-24 Degussa Ag Feuille a base d'un melange de polyamides
DE102007003327A1 (de) 2007-01-17 2008-07-24 Evonik Degussa Gmbh Mehrschichtfolie und daraus hergestelltes Verbundteil
WO2009156368A1 (fr) 2008-06-24 2009-12-30 Evonik Degussa Gmbh Composant avec couche de couverture constituée d’une matière moulable pa613

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DE2734294A1 (de) * 1977-07-29 1979-02-08 Basf Ag Schichtstoffe
EP0177829A2 (fr) * 1984-09-26 1986-04-16 Dai Nippon Insatsu Kabushiki Kaisha Film de base pour conformité tridimensionnelle
EP0288972A2 (fr) * 1987-04-27 1988-11-02 Mitsubishi Gas Chemical Company, Inc. Structure multicouche barrière aux gaz
EP0326355A2 (fr) * 1988-01-25 1989-08-02 Du Pont Canada Inc. Procédé de moulage par injection d'articles multicouches
EP0371743A2 (fr) * 1988-11-28 1990-06-06 Mitsui Petrochemical Industries, Ltd. Articles stratifiés moulés et procédés pour leur fabrication

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
DE2734294A1 (de) * 1977-07-29 1979-02-08 Basf Ag Schichtstoffe
EP0177829A2 (fr) * 1984-09-26 1986-04-16 Dai Nippon Insatsu Kabushiki Kaisha Film de base pour conformité tridimensionnelle
EP0288972A2 (fr) * 1987-04-27 1988-11-02 Mitsubishi Gas Chemical Company, Inc. Structure multicouche barrière aux gaz
EP0326355A2 (fr) * 1988-01-25 1989-08-02 Du Pont Canada Inc. Procédé de moulage par injection d'articles multicouches
EP0371743A2 (fr) * 1988-11-28 1990-06-06 Mitsui Petrochemical Industries, Ltd. Articles stratifiés moulés et procédés pour leur fabrication

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705255A (en) * 1994-07-29 1998-01-06 Grazioli S.P.A. Method and an apparatus for making a graphic representation on objects made of a polyolefin polymer and film for implementing said method
EP0694377A3 (fr) * 1994-07-29 1996-06-05 Graziola Spa Procédé et apparail pour la réalisation d'une représentation graphique sur un objet en polyoléfine et film utilisé dans ce procédé
EP0995571A4 (fr) * 1998-02-27 2003-01-29 Nissha Printing Feuille pour decoration dans le moule et article decore dans le moule
US6652983B1 (en) 1998-02-27 2003-11-25 Nissha Printing Co., Ltd. Sheet for in-mold decorating and in-mold decorated article
JP2000153536A (ja) * 1998-11-24 2000-06-06 Nissha Printing Co Ltd インサートフィルム
FR2804364A1 (fr) * 2000-02-02 2001-08-03 Plastic Omnium Cie Procede de fabrication d'une piece en matiere plastique comportant un film decoratif, et piece ainsi obtenue
EP1122049A1 (fr) * 2000-02-02 2001-08-08 Compagnie Plastic Omnium Procédé de fabrication d'une pièce en matière plastique comportant un film décoratif, et pièce ainsi obtenue
WO2006087250A1 (fr) * 2005-02-19 2006-08-24 Degussa Ag Feuille a base d'un melange de polyamides
KR100869430B1 (ko) * 2005-02-19 2008-11-21 에보니크 데구사 게엠베하 폴리아미드 블렌드 필름
RU2382796C2 (ru) * 2005-02-19 2010-02-27 Дегусса Гмбх Пленка для покрытия наружных поверхностей, применение формовочной массы и комбинированная деталь, состоящая из пленки и субстрата
US8614005B2 (en) 2005-02-19 2013-12-24 Evonik Degussa Gmbh Polyamide blend film
DE102007003327A1 (de) 2007-01-17 2008-07-24 Evonik Degussa Gmbh Mehrschichtfolie und daraus hergestelltes Verbundteil
WO2009156368A1 (fr) 2008-06-24 2009-12-30 Evonik Degussa Gmbh Composant avec couche de couverture constituée d’une matière moulable pa613
DE102008002599A1 (de) 2008-06-24 2009-12-31 Evonik Degussa Gmbh Bauteil mit Deckschicht aus einer PA613-Formmasse

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