WO2003000493A1

WO2003000493A1 - Multilayered colored sheet

Info

Publication number: WO2003000493A1
Application number: PCT/JP2001/005241
Authority: WO
Inventors: Atushi Araki; Hirofumi Yamada; Kazunori Kobashi; Hiroyuki Sato; Kosuke Arai
Original assignee: Dainippon Ink And Chemicals, Inc.
Priority date: 2000-07-27
Filing date: 2001-06-20
Publication date: 2003-01-03

Abstract

A multilayered colored sheet having a multilayer structure comprising: (A) a multilayered colored stretched sheet which comprises (a1) a thermoplastic resin layer containing a colorant dispersed therein and, superposed on at least one side thereof, (a2) a transparent thermoplastic resin layer and which has a transverse-direction heat contraction stress of 0.22 to 2.0 MPa and a machine-direction heat contraction stress of 0.22 to 2.0 MPa; and (B) a rubber-containing thermoplastic resin base sheet on which the sheet (A) is superposed. It is excellent in gloss, color, and impact strength.

Description

Specification

Technical field of multilayer colored sheet

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. Background art

Most automotive exterior parts such as bumpers and spoilers, motorcycle exterior parts such as cowling, OA equipment, and household electrical appliances are molded by injection molding.However, in most cases, heat is applied from the viewpoint of design and scratch resistance. The paint is applied by spraying a curable resin paint onto the molded body and then baking to crosslink.

Because of this, 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.

In recent years, as a method of solving and mitigating such problems, there has been a method of coating without a paint layer such as a composite paint coat obtained by laminating a backup sheet on a synthetic resin coated with a transparent layer, a coloring layer and an adhesive layer. However, this method does not solve the problem of environmental protection because a volatile organic solvent is used in the composite paint coating manufacturing process.In addition, this method does not solve the problem of transparent layer, colored layer and adhesive layer. Since it is not possible to make the thickness of the product sufficiently large, when manufacturing a molded product such as an automotive exterior member that is complex and has a large drawing ratio by thermoforming, it is difficult to achieve gloss spots, color spots, and various factors required for the final molded article. There was a problem that the adhesive strength between the layers could not be obtained.

Therefore, conventionally, for example, 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.

However, the technique described in 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.

That is, in 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. OMPa multi-layer colored stretched sheet (A) laminated on rubber-containing thermoplastic resin base sheet (B) The present invention relates to a multilayer colored sheet having the following. BEST MODE FOR CARRYING OUT THE INVENTION

As described above, 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).

That is, for the multilayer colored stretched sheet (A) that forms a surface layer when formed into a molded product, the heat shrinkage stress in the TD direction 0.22 to 2. OMPa, the heat shrinkage stress in the MD direction 0.22 to 2. OMPa By doing so, 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. In the present invention, 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. In particular, 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). In particular, a transparent thermoplastic resin layer is provided on both sides of the colorant-dispersed thermoplastic resin layer (a 1).

It is preferable that 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.

Here, 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.

Examples of the thermoplastic acrylic polymer 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.

Among them, 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.

When 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.

These 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. .

Next, as the colorant contained in the colorant-dispersed thermoplastic resin layer (a 1), any of various pigments and dyes can be used. For example, a natural pigment type, a chromate type, a fluoridated type, and the like can be used. , Oxides, sulfides, sulfates, silicates, metal powders, chrome greens, natural dye lakes, nitroso pigments, nitro pigments, azo pigments, basic dye lakes , Mordant dye pigments, vat dye pigments, phthalocyanine pigments, fluorescent pigments, azine pigments, basic dyes, acid dyes, fluorescent dyes, monoazo dyes, anthraquinone dyes, azine dyes, base dyes, Acid dyes, metal complex compound dyes and the like can be mentioned.

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.

Here, 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. These additives may be used alone or in combination of two or more.

In addition, the colorant-dispersed thermoplastic resin layer (a 1) does not impair the impact properties and moldability. Within the range, scaly aluminum powder, colored titanium, glittering agents such as My power, and concealing agents (fillers) such as titanium oxide and clay may be added.

Next, the 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.

Examples of the transparent thermoplastic acrylic polymer 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.

Among these, 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. If the constituent material of the colorant-dispersed 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.

Specifically, when both the colorant-dispersed thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2) are acrylic polymers, after melt-kneading in an extruder, the temperature is 200 to 280 ° C. Co-extrusion under temperature conditions, and then, while cooling the formed sheet, stretching is performed in the MD direction at a roll temperature of 110 to 135 ° C due to the speed difference between the rolls. The method of stretching under a temperature condition of 20 to 140 ° C is preferred.

Regarding the thickness of the colorant-dispersed thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2), 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.

Next, 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. In other words, by using 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. For example, ethylene-propylene copolymer rubber, ethylene-propylene-gen copolymer rubber, ethylene-butene-11 copolymer rubber, Acrylonitrile or methacrylic acid ester on rubbery polymers such as propylene butene-1 copolymer rubber And a graft copolymer of styrene and acrylonitrile to a rubber-like polymer.

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.

Among these, 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). For example, 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. For example, by using 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.

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. In this case, specifically, 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 X m / p

(Where X is one color selected from 丫, GY, G, BG, B, PB, P, RP, R, YR, and N, n is 1 to 10, m is 0 to 10, p must have the same X in the hue represented by 0 to 38), and satisfy the condition that the difference between the values of n is 2 or less and the difference between the values of m and p is 5 or less, respectively. Is preferred because it facilitates adjustment to the desired hue.

Note that the hue composed of から, 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. Furthermore, 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

(m) 0 to 10 and the p-value is a value obtained by dividing the achromatic color to 0 and dividing it into equal rates in accordance with the increase in the degree of shading, and (P) 0 to 38.

In particular, 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. In 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. Next, 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. After blending additives, fillers, etc., 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.

Here, “substantially no stretching” refers to a state in which the practical orientation is extremely low.Specifically, the heat shrinkage stress in the TD direction is 0.IMPa or less, and the heat shrinkage stress in the MD direction is 0. It is preferably at most 1 MPa.

The ratio of the thickness of the multilayer colored stretched sheet (A) to the thickness of the rubber-containing thermoplastic sheet (B) is as follows: (B) (A) = 1 Z (0.1-1) It is preferable because the design properties of the colored stretched sheet (A) are maintained and the thermal processability of the multilayer colored sheet of the present invention is improved.

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.

As a laminating method, it is also possible to co-extrude a multilayer colored stretched sheet (A) and a rubber-containing thermoplastic resin base sheet (B).

The manufacturing method of the laminating process is not particularly limited. Push A lamination method and an adhesive tape lamination method are preferred.

Among them, a co-extrusion lamination method and a heat lamination method are preferred from the viewpoint of adhesive strength.

When the wet lamination method, the dry lamination method, the solventless dry lamination method, the hot melt lamination method, or the like is used, 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).

When the multilayer stretched sheet (A) and the rubber-containing thermoplastic resin base sheet (B) of the present invention are laminated with an adhesive layer (C) provided thereon, starch that can be used as a main component is 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. Among these, a thermosetting resin adhesive or a thermoplastic resin adhesive is preferred from the viewpoint of adhesive strength.

Further, the multilayer colored sheet of the present invention described in detail above may be further provided with a protective film on its surface. Here, 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. As the thermoforming, 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

Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited thereto. The evaluation of various physical properties in each of Examples and Comparative Examples was performed according to the following methods.

Evaluation method

(1) Gloss

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.

(2) Color

The Munsell color chart manufactured by Nippon Denshoku Industries Co., Ltd. was evaluated based on JIS-Z8721.

(3) Accelerated weather resistance

After exposing the formed laminated sheet for 500 hours with Ubucon manufactured by Toyo Seiki Seisaku-sho, the change in gloss was evaluated.

(4) Heat shrinkage stress

Indirect heating was performed between two hot plates heated to 200 ° C (5 gaps) by our method, and the contraction stress was measured.

(5) Folding strength

The bending strength was evaluated by a MIT test in accordance with JIS-P8115.

(6) Impact resistance

Impact resistance was evaluated by a dart impact test based on JI S-K7 124. (7) Color hiding factor

For the multilayer colored sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 3, using the color difference in the L * a * b * color system manufactured by Nippon Denshoku Industries Co., Ltd. based on JI SZ 7124, Was evaluated by the following method.

The value of the color difference of the multi-layered colored sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the color difference of a sheet obtained by laminating a Munsell color [V く 1 (black)〗] sheet on the back surface of the sheet. From the values, when the former value was set to 100, the latter value was defined as the color hiding ratio. Next, the color difference of the molded product was measured for a multilayer colored sheet in which a Munsell color [V1 (black)] sheet was laminated on the back surface, and the color concealment ratio was calculated in the same manner.

Example 1

As a resin component forming the colorant-dispersed thermoplastic resin layer (a 1), 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.)

Using “MG5”), 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.

(Layer structure)

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

On the other hand, as a resin component forming the rubbery thermoplastic resin layer (B), 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 」Η 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 of “AS-106J and“ LR-100 ”manufactured by Dainippon Ink and Chemicals, Inc.) that has the following layer configuration A colored sheet was manufactured. Tables 1 and 2 show the results of various evaluations.

(Layer structure)

Multi-layer colored stretched sheet (A 1) 20 O jUm

Resin adhesive (C) 5 rn

Base sheet (B 1) 300 jt m

Example 2

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.

(Layer structure)

Multi-layer colored stretched sheet (A 2) 200 jUm

Resin adhesive (C) 5 m

Base sheet (B1) 300 m

Example 3

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.

(Layer structure)

Multi-layer colored stretched sheet (A3) 200jt m

Resin adhesive (C) 5 im

Base material sheet (B 1) 300 jU m

Comparative Examples 1-3

From the colorant-dispersed thermoplastic resin layer (a 1) and the transparent thermoplastic resin layer (a 2) in Examples 1 to 3, the same layer constitution as the multilayer colored stretched sheets (A 1) to (A 3), respectively. And multi-layer colored stretched sheets (A6) to (A8) having a heat shrinkage stress of 0.1 MPa in both the MD direction and the TD direction were obtained, and in the same manner as in Examples 1 to 3, A multilayer colored sheet having the following layer configuration was manufactured. Tables 1 and 2 show the results of various evaluations.

(Layer structure)

Multi-layer colored stretched sheet (A6)-(A8) 200 jt / m

Resin adhesive (C) 5 ^ m

Substrate sheet (B 1) 300 ju m

9

so / iodf / e :) d £ 6t000 / £ 0 OAV Table 2

Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, 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.

Therefore, 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.

Claims

The scope of the claims

1. A transparent thermoplastic resin layer (a2) is laminated on at least one layer of the colorant-dispersed thermoplastic resin layer (a1). The heat shrinkage stress in the TD direction is 0.22 to 2. a, and heat shrinkage stress in MD direction 0.22 to 2. Multilayer colored stretch sheet (A) of OM Pa is laminated on rubber-containing thermoplastic resin base sheet (B). A multilayer colored sheet characterized by having.

2. The multilayer colored stretched sheet (A) has a structure in which a transparent thermoplastic resin layer (a 2) is disposed on both surface layers of the colorant-dispersed thermoplastic resin layer (a 1). Item 2. The multilayer colored sheet according to item 1.

3. The ratio (a 1) (a 2) of one thickness of the colorant-dispersed thermoplastic resin layer (a 1) to one thickness of the transparent thermoplastic resin layer (a 2) is 1 (0. The multilayer colored sheet according to claim 1, which is in the range of "! To 2).

4. The multilayer colored sheet according to claim 2, wherein the multilayer colored stretched sheet (A) is produced by co-extrusion of a colorant-dispersed thermoplastic resin and a transparent thermoplastic resin layer.

5. The multilayer colored sheet according to claim 1, wherein the rubber-containing thermoplastic resin base sheet (B.) contains a coloring agent.

6. The multi-layer colored stretched sheet (A) alone has a hue and a rubber-containing thermoplastic resin base sheet containing a colorant (B) has a hue based on the following formula that conforms to JIS Z 8721.

n X mZ p

(Where X is one hue selected from Y, GY, G, BG, B, PB, P, RP, R, YR and N, n is 1 to 10, m is 0 to 10, (p is from 0 to 38). The multi-layered color sheet according to claim 5.

7. The content of the colorant in the colorant-dispersed thermoplastic resin layer (a1) is 5 to 20% by weight. 7. The multilayer colored sheet according to claim 6, wherein the content of the colorant in the colorant-dispersed rubber-containing thermoplastic resin base sheet (B) is 5 to 30% by weight.

8. The colorant-dispersed thermoplastic resin layer (a 1) is mainly composed of a rubber-containing acrylic resin, and the transparent thermoplastic resin layer (a 2) is a rubber-free acrylic resin. 3. The multilayer colored sheet according to claim 2, which is mainly composed of a rill-based resin.

9. The thickness ratio between the multilayer colored stretched sheet (A) and the rubber-containing thermoplastic resin base sheet (B) (B) No (A) is 1 (0.1 to 1). The multilayer coloring sheet described in Item 8.

10. The multilayer coloring according to claim 4, wherein the multilayer coloring stretched sheet (A) and the rubbery thermoplastic resin base sheet (B) are laminated and manufactured by an adhesive layer (C). Sheet.