WO2003000493A1 - Feuille coloree multicouches - Google Patents

Feuille coloree multicouches Download PDF

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Publication number
WO2003000493A1
WO2003000493A1 PCT/JP2001/005241 JP0105241W WO03000493A1 WO 2003000493 A1 WO2003000493 A1 WO 2003000493A1 JP 0105241 W JP0105241 W JP 0105241W WO 03000493 A1 WO03000493 A1 WO 03000493A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
sheet
colorant
multilayer
rubber
Prior art date
Application number
PCT/JP2001/005241
Other languages
English (en)
Japanese (ja)
Inventor
Atushi Araki
Hirofumi Yamada
Kazunori Kobashi
Hiroyuki Sato
Kosuke Arai
Original Assignee
Dainippon Ink And Chemicals, Inc.
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
Priority to JP2000226282A priority Critical patent/JP2001239622A/ja
Priority claimed from JP2000226282A external-priority patent/JP2001239622A/ja
Application filed by Dainippon Ink And Chemicals, Inc. filed Critical Dainippon Ink And Chemicals, Inc.
Priority to PCT/JP2001/005241 priority patent/WO2003000493A1/fr
Publication of WO2003000493A1 publication Critical patent/WO2003000493A1/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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents

Definitions

  • the present invention relates to a multilayer colored sheet excellent in gloss and impact resistance, particularly a multilayer colored sheet useful as a coating-less sheet for exterior members of automobiles, motorcycles, office automation equipment, home appliances and the like.
  • the paint is applied to the plastic injection molded body through several stages of coating processes and dried in a drying facility, so the coating cost is high and there are concerns about environmental problems such as the emission of volatile organic solvents during drying. Is done.
  • Japanese Patent Application Laid-Open No. 10-291282 discloses a transparent polymethyl methacrylate layer containing acryl rubber as a surface layer on a special colorant-containing support layer, Gloss and impact strength by forming a laminated sheet with a polymethyl methacrylate resin layer containing a colorant as an intermediate layer between the resin and the surface layer Are disclosed.
  • Japanese Patent Application Laid-Open No. 10-291282 can solve the problems of appearance such as gloss spots and color spots, but is inferior in impact strength when formed into a final molded product. In this case, there was a problem that the stones were easily whitened due to flying pebbles and the like and light contact.
  • the problem to be solved by the present invention is to provide a multilayer colored sheet which is excellent in gloss and color, and which is remarkably excellent in impact strength. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, by laminating a multilayer colored sheet having a specific heat shrinkage stress orientation on a rubber-containing thermoplastic resin base sheet, The inventors have found that the impact strength of a final molded product can be dramatically improved, and have completed the present invention.
  • the transparent thermoplastic resin layer (a 2) is laminated on at least one side of the colorant-dispersed thermoplastic resin layer (a 1), and the heat shrinkage stress in the TD direction is 0.22 to 2.
  • OMPa and heat shrinkage stress in MD direction 0.22 to 2.
  • the present invention relates to a multilayer colored sheet having the following. BEST MODE FOR CARRYING OUT THE INVENTION
  • the multilayer colored sheet of the present invention has a heat shrinkage stress in the TD direction of 0.22 to 2.
  • OMPa and a heat shrinkage stress in the MD direction of 0.22 to 2.
  • Multilayer coloring of OMPa It has a structure in which the stretched sheet (A) is laminated on the rubber-containing thermoplastic resin base sheet (B).
  • the heat shrinkage stress in the TD direction 0.22 to 2.
  • the heat shrinkage stress in the MD direction 0.22 to 2.
  • excellent impact resistance can be developed. Specifically, in both the TD and MD directions, the heat shrinkage stress was 0.22 MPa If it is full, the orientation of the multilayer colored stretched sheet (A) is not sufficient and the impact resistance is low. On the other hand, if it is larger than 2 OMPa, excessive orientation may cause breakage at the time of molding, and the gloss may be significantly reduced.
  • the heat shrinkage stress of the multilayer colored stretched sheet (A) may be appropriately adjusted according to required quality from the above range, and may be adjusted particularly according to thermoformability, glossiness and impact strength.
  • it is preferably 0.5 to 1.3 MPa in both the TD direction and the MD direction from the viewpoint of excellent balance between thermoformability, gloss, and impact strength.
  • the multilayer colored stretched sheet (A) may have a transparent thermoplastic resin layer (a 2) on at least one side of the colorant-dispersed thermoplastic resin layer (a 1).
  • a transparent thermoplastic resin layer is provided on both sides of the colorant-dispersed thermoplastic resin layer (a 1).
  • the structure has (a2). That is, when the transparent thermoplastic resin layer (a2) is provided only on one side, the multilayer colored stretched sheet (A) is likely to be warped immediately after the production. Therefore, by arranging the transparent thermoplastic resin layers (a 2) on both sides, this warpage is prevented, and the bonding between the multilayer colored stretched sheet (A) and the rubber-containing thermoplastic resin base sheet (B) can be performed. In addition to being easier, the adhesive strength between the multilayer colored stretched sheet (A) and the rubber-containing thermoplastic resin base sheet (B) will be dramatically improved.
  • the resin component constituting the colorant-dispersed thermoplastic resin layer (a1) is not particularly limited, but is preferably a thermoplastic acryl-based polymer due to its weather resistance and ultraviolet shielding effect. is there.
  • thermoplastic acrylic polymer examples include homopolymers of acrylic acid, acrylate ester, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile and the like, or copolymers containing these as main components. Specifically, polymethyl acrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-methyl methacrylate copolymer, polyacrylonitrile, acrylonitrile monostyrene In addition to copolymers of acrylonitrile and methyl methacrylate, copolymers of acrylonitrile or methacrylate on rubbery polymers are listed. I can do it.
  • a homopolymer of methyl methacrylate or acrylonitrile, or a copolymer containing these as a main component is particularly preferred because of its remarkably excellent weather resistance and ultraviolet shielding effect.
  • a pigment-based colorant is used in the colorant-dispersed thermoplastic resin layer (a 1)
  • seed polymerization is carried out in view of the reduced impact resistance due to its addition and the weather resistance when used outdoors. It is preferable to use a rubber-reinforced polymethyl methacrylate polymer in which a multi-structure crosslinked acryl-based rubber is dispersed.
  • thermoplastic acrylic polymers may be blended with other polymers and additives such as polyvinylidene fluoride, polycarbonate, etc., as long as they do not impair the colorability, physical properties, and moldability. .
  • any of various pigments and dyes can be used as the colorant contained in the colorant-dispersed thermoplastic resin layer (a 1).
  • a natural pigment type, a chromate type, a fluoridated type, and the like can be used as the colorant contained in the colorant-dispersed thermoplastic resin layer (a 1).
  • the additive of the coloring agent to be blended with the thermoplastic acryl-based polymer is not particularly limited, but is 0.1 to 20% by weight in terms of hue and underlying color concealment, and impact strength. It is preferable that it is in the range of 0.5 to 15% by weight.
  • ultraviolet absorbers antioxidants, antiozonants, activators, and additives such as vulcanization accelerators and vulcanization accelerators are combined as long as the impact strength and moldability are not impaired. May be.
  • additives may be used alone or in combination of two or more.
  • the colorant-dispersed thermoplastic resin layer (a 1) does not impair the impact properties and moldability.
  • scaly aluminum powder, colored titanium, glittering agents such as My power, and concealing agents (fillers) such as titanium oxide and clay may be added.
  • thermoplastic resin constituting the transparent thermoplastic resin layer (a 2) is not particularly limited, but the interlayer adhesion with the colorant-dispersed thermoplastic resin layer (a 1) and the molded article From the viewpoint of excellent durability, a transparent thermoplastic acryl-based polymer is preferred.
  • the transparent thermoplastic acrylic polymer examples include, for example, homopolymers such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile, and copolymers containing these as a main component, Specifically, polymethyl acrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-ethyl methacrylate copolymer, polyacrylonitrile, acrylonitrile-styrene Copolymers and acrylonitrile methyl methacrylate copolymer.
  • homopolymers such as acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile, and copolymers containing these as a main component
  • a homopolymer of methyl methacrylate or acrylonitrile, or a copolymer containing these as a main component is excellent in weather resistance, ultraviolet shielding property and transparency, and has a colorant-dispersed thermoplastic resin layer ( It is preferable to use the same type of thermoplastic resin for a1), since the interlayer adhesiveness and the durability of the molded product are dramatically increased.
  • the transparent thermoplastic resin layer (a 2) must have a light transmittance of 80% or more in the (a 2) -layer, so that the colorant-dispersed thermoplastic resin layer (a 1) has a three-dimensional appearance. It is preferable from the viewpoint of improving the feel (depth) and surface gloss, protecting the colorant-dispersed thermoplastic resin layer (a 1) and imparting surface functionality.
  • the method for producing the multi-layer colored stretched sheet (A) composed of the above-mentioned colorant-dispersed thermoplastic resin layer (a 1) and transparent thermoplastic resin layer (a 2) is not particularly limited.
  • the raw material components of the colorant-dispersed thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2) are melt-kneaded in each extruder, and each layer is fed to a T-die. More specifically, a method may be used in which two or two layers or two or three layers are cooled using a co-extrusion molding roll and then stretched in the MD and TD directions.
  • thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2) are significantly different in fluidity and the layer distribution is not uniform, co-extrusion has multi-manifold.
  • a T-die can also be used.
  • both the colorant-dispersed thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2) are acrylic polymers
  • the temperature is 200 to 280 ° C.
  • the method of stretching under a temperature condition of 20 to 140 ° C is preferred.
  • the thicknesses of (a 1) and (a 2) are determined from the viewpoint of the balance between hue and mechanical strength. It is preferable that the thickness ratio (a 1) (a 2) of the transparent thermoplastic resin layer (a 2) is 1 / (0. "! To 2), and the transparent thermoplastic resin layer (a 2) has a deep color. It is particularly preferable that the thickness ratio (a 1) (a 2) is in the range of 1 Z (0.5 to 2) from the viewpoint of further improving the gloss.
  • the thickness of the multi-layered colored stretched sheet (A) is not particularly limited, but the thinner the sheet, the better the formability. On the other hand, the thicker the sheet, the better the impact strength. From the viewpoint of this performance balance, the range is preferably from 50 to 400 / m, and particularly preferably from 100 to 300 m.
  • the rubber-containing thermoplastic resin base sheet (B) on which the multilayer colored stretched sheet (A) is laminated has a rubber-containing thermoplastic resin as a main component.
  • a rubber-containing thermoplastic resin when applied to a deep drawn product having a complicated shape such as an automobile exterior part, it can have excellent shapeability and exhibit excellent impact strength.
  • Such a rubber-containing thermoplastic resin is not particularly limited.
  • the rubber-containing thermoplastic resin base sheet (B) is used for the adhesiveness of each part or molded article to the base material or the molding method of each part or molded article, and the adhesiveness to the multilayer colored stretched sheet (A). It is preferable to select appropriately from the viewpoint.
  • a graft copolymer of styrene and acrylonitrile to a rubber-like polymer specifically, an acrylonitrile-butadiene-styrene copolymer is preferable from the viewpoint of thermoformability.
  • the rubber-containing thermoplastic resin base sheet (B) may be uncolored, of course, but in the present invention, it is preferable that the coloring agent is contained so that the base color of the final molded article is excellent in concealing properties. This is preferable because
  • the colorant that can be used here is not particularly limited, but various pigments and dyes can be used as in the case of the multilayer colored stretched sheet (A).
  • various pigments and dyes can be used as in the case of the multilayer colored stretched sheet (A).
  • natural pigments Chromate type, fluoric acid type, oxide type, sulfide type, sulfate type, silicate type, metal powder type, chrome green type, natural dye lake type, nitroso type pigment, nitro type pigment, azo type Pigment, basic dye lake type, mordant dye type pigment, vat dye type pigment, phthalocyanine type pigment, fluorescent pigment, azine type pigment, basic dye, acid dye, fluorescent dye, monoazo type dye, anthraquinone type dye, azine Dyes, base dyes, acid dyes, metal complex compound dyes, and the like.
  • the content of the colorant in the rubber-containing thermoplastic resin is from 0.1 to 20% by weight from the viewpoint of maintaining hue and polymer properties. / o is preferable, and particularly preferably 0.5 to 15% by weight.
  • the selection of the coloring agent in the rubber-containing thermoplastic resin base sheet (B) is not particularly limited.
  • coloring agents having different hues of the multilayer coloring sheet A subtle hue may be developed due to the difference in color between the sheet (A) and the sheet (B), or a metallic or specular gloss may be obtained by using a metal powder colorant. . That is, the colorant in the sheet (A) and the sheet (B) may be appropriately selected according to the intended design. In addition, either one of the sheet (A) and the sheet (B) or both may be used. A pattern may be formed.
  • the sheet (A) When the multilayer colored sheet according to the present invention is used by being laminated on a base material made of metal, resin, or the like, the sheet (A) may be used to conceal the base color of the base material and develop a single color with good hue. ) And the sheet (B) are preferably the same color.
  • the hue of the multilayer colored stretched sheet (A) alone and the rubber-containing thermoplastic resin base sheet containing the colorant ( B) The hue in a single unit is the following formula based on JISZ 8721.
  • n 1 to 10
  • m 0 to 10
  • p must have the same X in the hue represented by 0 to 38
  • Is preferred because it facilitates adjustment to the desired hue.
  • the hue composed of ⁇ ⁇ , GY, G, BG, B, PB, P, RP, R, YR and N represented by X in the above formula are red (R), yellow (Y), and green (G ), Blue (B) and purple (P) are basic hues, and these intermediate hues are indicated by YR, GY, BG, PB and RP.
  • the n value is a value divided so that the difference in hue sensation is equal, and is indicated by (n) 1 to 10.
  • the m value is 0 when ideal black is 10 and ideal white is 10. The value divided so that the difference in the sense of brightness is equal
  • the difference between the hue of the multi-layer colored stretched sheet (A) alone and the hue of the rubber-containing thermoplastic resin base sheet containing the colorant (B) alone is the difference between the n values in the above equation. Is preferably 1 or less, and the difference between the m value and the p value is 3.0 or less.
  • the rubber-containing thermoplastic resin base sheet (B) additives, fillers and the like may be blended as long as the impact strength and moldability are not impaired.
  • the method for producing the rubber-containing thermoplastic resin base sheet (B) is not particularly limited, but a coloring agent, if necessary, may be added to the rubber-containing thermoplastic resin.
  • melt kneading in each extruder and extruding a film from a T-die are used.
  • the extrusion temperature at this time is not particularly limited, but is 230 to 280. ° C.
  • the thickness of the rubber-containing thermoplastic resin base sheet (B) is 75 to 1 000 jt in order to maintain the shape of the multilayer colored sheet during thermoforming and to suppress breakage due to injection pressure during injection molding. / m, particularly preferably 200 to 500 m. Further, the rubber-containing thermoplastic resin base sheet (B) is preferably substantially non-elongated from the viewpoint of moldability, and particularly in the use of automobile exterior parts, the shape becomes complicated and deep drawing is performed. Therefore, it is particularly important that the film is not drawn substantially.
  • substantially no stretching refers to a state in which the practical orientation is extremely low.
  • the heat shrinkage stress in the TD direction is 0.IMPa or less
  • the heat shrinkage stress in the MD direction is 0. It is preferably at most 1 MPa.
  • the method of laminating the multilayer colored stretched sheet (A) and the rubber-containing thermoplastic resin go material sheet (B) is not particularly limited, but the multilayer stretched sheet (A) and the rubber are laminated.
  • the manufacturing method is preferable in which the thermoplastic resin base sheet (B) is bonded.
  • the manufacturing method of the laminating process is not particularly limited. Push A lamination method and an adhesive tape lamination method are preferred.
  • a co-extrusion lamination method and a heat lamination method are preferred from the viewpoint of adhesive strength.
  • the multilayer stretched sheet (A) and the rubber-containing thermoplastic resin substrate sheet are used. It is preferable to provide an adhesive layer (C) between the adhesive layer and (B).
  • starch that can be used as a main component is starch starch.
  • starch starch Dextrin, glue, casein, soy protein, asphalt, and other natural adhesives; phenol resin adhesives, resorcinol resin adhesives, phenol-resorcinol resin adhesives, epoxy resin adhesives, urea resin adhesives
  • Thermosetting resin adhesives such as adhesives, polyurethane adhesives, and polyaromatic adhesives
  • vinyl acetate resin, acrylic resin, ethylene vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon, shear Thermoplastic resin-based adhesives such as acrylate resins; black-mouthed prene-based adhesives, nitrile rubber-based adhesives, SB Rubber-based adhesives such as R-based adhesives and natural rubber-based adhesives are exemplified.
  • the multilayer colored sheet of the present invention described in detail above may be further provided with a protective film on its surface.
  • the protective film is to be attached immediately after the formation of the multilayer colored sheet to prevent scratches during storage and transportation of the multilayer colored sheet.
  • Such a protective film is not particularly limited, but a film made of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, or the like can be preferably used.
  • the colored multilayer sheet thus obtained is usually thermoformed into a preform having a three-dimensional shape.
  • a forming means such as vacuum forming, pressure forming, vacuum pressure forming or the like is preferably employed, but vacuum forming is particularly convenient and preferable.
  • the surface temperature of the colored multilayer sheet during vacuum forming is not particularly limited, but is preferably in a range of 5 ° C to 20 ° C higher than the Tg of the resin or polymer constituting each layer. .
  • the preformed body obtained in this manner is inserted into an injection mold and then subjected to injection molding on the backup layer (B) to be used for exterior parts such as automobiles, motorcycles, OA equipment, and home appliances. it can.
  • Example 1 The preformed body obtained in this manner is inserted into an injection mold and then subjected to injection molding on the backup layer (B) to be used for exterior parts such as automobiles, motorcycles, OA equipment, and home appliances. it can.
  • the co-extruded multilayer stretched laminated sheet was evaluated based on the regular reflectance of incident light at an angle of 45 degrees in accordance with JIS-K710.
  • the Munsell color chart manufactured by Nippon Denshoku Industries Co., Ltd. was evaluated based on JIS-Z8721.
  • Indirect heating was performed between two hot plates heated to 200 ° C (5 gaps) by our method, and the contraction stress was measured.
  • the bending strength was evaluated by a MIT test in accordance with JIS-P8115.
  • polymethyl methacrylate (trade name “HT03 Y”) manufactured by Sumitomo Chemical Co., Ltd. was compared with quinophthalone yellow 3.8 phr and calcined titanium yellow 2 A mixture of a pigment consisting of 9 phr and highly dispersed titanium white 3.8 phr, and a dispersant consisting of 3.8 phr of acrylic acid-styrene copolymer (average molecular weight 15000) and 0.7 phr of magnesium stearate (15 phr) kneaded and dispersed, and on the other hand, as a resin component for forming the transparent thermoplastic resin layer (a 2), polymethyl methacrylate (trade name, manufactured by Sumitomo Chemical Co., Ltd.)
  • each raw material resin was extruded at 260 ° C using two extruders, and two types and three layers were laminated by a feed block, and a non-stretched raw film was formed from a T die. After that, it is stretched with a roll at 120 ° C and a tenter at 130 ° C and wound up by a winder, and has a heat shrinkage stress of 1.18MP in the MD and TD directions with the following layer structure.
  • a multilayer colored stretched sheet (A 1) was obtained.
  • Multi-layer colored stretched sheet (A) 200 jU m (2 types 3 layers)
  • Transparent thermoplastic resin layer (a 2) 50 m
  • Colorant dispersed thermoplastic resin layer (a1) 100 m
  • Transparent thermoplastic resin layer (a 2) 50 m
  • Japan A & A Pigment consisting of 1 phr of quinophthalone yellow, 3.8 phr of calcined titanium yellow and 6.4 phr of highly dispersed titanium white, and 1 styrene of acrylic acid monostyrene, compared to L resin ABS resin (trade name ⁇ 2) Copolymer (Average molecular weight: 15,000) Kneading and dispersing a mixture (13 phr) of a dispersant consisting of 1 pr and 0.8 phr magnesium stearate Melt kneading in an extruder at 260 ° C To obtain a substantially unstretched base sheet (B 1) having a thickness of 300 Wm, and then the multi-layer colored stretched sheet (A 1) and the base sheet (B 1) are subjected to two-pack A laminating process using a urethane-based adhesive (a two-component mixed adhesive consisting
  • Multi-layer colored stretched sheet (A 1) 20 O jUm
  • Example 1 In the same manner as in Example 1 except that the transparent thermoplastic resin layer (a 2) in Example 1 was kneaded by blending 50% of “U40F” (acrylonitrile-styrene-acrylic acid copolymer) manufactured by Mitsubishi Rayon Co., Ltd. A multilayer colored stretched sheet (A2) having a heat shrinkage stress of 0.65 MPa in both the MD and TD directions was obtained, and a multilayer colored sheet having the following layer configuration was manufactured in the same manner as in Example 1. . Tables 1 and 2 show the results of various evaluations.
  • U40F acrylonitrile-styrene-acrylic acid copolymer
  • Example 1 Except that 50% of "IRS704" (rubber modified polymethyl methacrylate) manufactured by Mitsubishi Rayon was kneaded in the transparent thermoplastic resin layer (a 2) in Example 1. Heat shrinkage stress in both MD and TD directions was obtained in the same manner as in Example 1. A multilayer colored stretched sheet (A3) of 1.8 MPa was obtained. A sheet was manufactured. Tables 1 and 2 show the results of various evaluations.
  • Multi-layer colored stretched sheet (A6)-(A8) 200 jt / m
  • the glossiness and color are excellent, and also the multilayer coloring sheet which is extremely excellent in impact strength can be provided. Furthermore, when a coloring agent is contained in the rubbery thermoplastic resin base sheet (B), the base color shielding property is also good.
  • the multilayer colored sheet of the present invention can be suitably used for automobile exterior members, office automation equipment, home electric appliances, building members, and the like.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille colorée multicouches présentant une structure comprenant: (A) une feuille multicouches étirée colorée constituée (a1) d'une couche de résine thermoplastique dans laquelle un colorant est dispersé, (a2) d'une couche de résine thermoplastique transparente superposée sur au moins un côté de l'autre couche; la feuille multicouches présente également une contrainte à la contraction thermique comprise entre 0,22 et 2,0 MPa dans le sens travers et une contrainte à la contraction thermique comprise entre 0,22 et 2,0 MPa; (B) une feuille à base de résine thermoplastique à teneur en caoutchouc sur laquelle la feuille (A) est superposée. Cette structure présente une excellente brillance, une excellente intensité des couleurs et une excellente résistance aux chocs.
PCT/JP2001/005241 1999-12-20 2001-06-20 Feuille coloree multicouches WO2003000493A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2000226282A JP2001239622A (ja) 1999-12-20 2000-07-27 多層着色シート
PCT/JP2001/005241 WO2003000493A1 (fr) 2000-07-27 2001-06-20 Feuille coloree multicouches

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000226282A JP2001239622A (ja) 1999-12-20 2000-07-27 多層着色シート
PCT/JP2001/005241 WO2003000493A1 (fr) 2000-07-27 2001-06-20 Feuille coloree multicouches

Publications (1)

Publication Number Publication Date
WO2003000493A1 true WO2003000493A1 (fr) 2003-01-03

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PCT/JP2001/005241 WO2003000493A1 (fr) 1999-12-20 2001-06-20 Feuille coloree multicouches

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WO (1) WO2003000493A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4228267A (en) * 1978-09-09 1980-10-14 Asahi-Dow Limited Methyl methacrylate-based resin film and sheet
JPH04214323A (ja) * 1990-12-12 1992-08-05 Asahi Chem Ind Co Ltd Ａａｓ系樹脂延伸シート及びフィルム
JPH10291282A (ja) * 1996-12-10 1998-11-04 Basf Ag 積層シート又はフィルム及びその成形体
JPH10305541A (ja) * 1997-03-06 1998-11-17 Toray Ind Inc ラミネート用二軸延伸ポリエステルフィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4228267A (en) * 1978-09-09 1980-10-14 Asahi-Dow Limited Methyl methacrylate-based resin film and sheet
JPH04214323A (ja) * 1990-12-12 1992-08-05 Asahi Chem Ind Co Ltd Ａａｓ系樹脂延伸シート及びフィルム
JPH10291282A (ja) * 1996-12-10 1998-11-04 Basf Ag 積層シート又はフィルム及びその成形体
JPH10305541A (ja) * 1997-03-06 1998-11-17 Toray Ind Inc ラミネート用二軸延伸ポリエステルフィルム

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