WO1997046383A1

WO1997046383A1 - Coextruded, multilayered laminated sheet and process for preparing plastic molding by using the same

Info

Publication number: WO1997046383A1
Application number: PCT/JP1997/001908
Authority: WO
Inventors: Izumi Ishii; Hitoshi Yamada
Original assignee: Mitsubishi Chemical Corporation
Priority date: 1996-06-06
Filing date: 1997-06-05
Publication date: 1997-12-11

Abstract

A coextruded, multilayered laminated sheet characterized by comprising a colored layer (A) comprising a colorant-containing thermoplastic acrylic polymer and/or thermoplastic fluororesin, a layer (B) comprising a modified olefin polymer containing at least one functional group selected from the group consisting of carboxyl, acid anhydride, hydroxyl, and glycidyl groups, and a backup layer (C) comprising an olefin polymer, the layers (A), (B) and (C) being laminated on top of another in the order of (A), (B) and (C). A process for preparing a plastic molding characterized by laminating a colored layer (A) comprising a colorant-containing thermoplastic acrylic polymer and/or thermoplastic fluororesin, a layer (B) comprising a modified olefin polymer containing at least one functional group selected from the group consisting of carboxyl, acid anhydride, hydroxyl, and glycidyl groups, and a backup layer (C) comprising an olefin polymer on top of one another by multilayer coextrusion in the order of (A), (B) and (C) to prepare a sheet, thermoforming the sheet to prepare a preform having a three-dimensional shape, inserting the preform into an injection mold, and then injection molding an olefin polymer so as to come into contact with the backup layer (C).

Description

Description Co-extruded multi-layer laminated sheet and method for producing plastic ¾B body using the same

Advantageous Effects of Invention The present invention can provide a coextruded multilayer laminated sheet having a specific layer configuration and excellent in gloss and color, and by using the same, can omit the use of a paint application and casting sheet. The present invention relates to a method for manufacturing a plastic fi ^ body, and particularly to a method for manufacturing an automobile exterior component.

Background technology

Most of the automotive exterior parts made of plastics such as Bamba and side moldings are made of S-acrylic melamine-based or acrylyl-isocyanate-based thermosetting resin paint because most of them are made by injection. After spray-painting the S¾¾ body, the paint is applied by baking to crosslink. In other words, after applying the paint through a multi-step process at the facility and drying it at the facility, painting is expensive, and volatile organic ^ PJ emissions during drying There was a problem that there was a concern of environmental protection. Various studies have been made to solve or alleviate such problems.For example, it is obtained by laminating a back-up sheet on a synthetic resin casting sheet coated with a transparent and adhesive layer. A method has been proposed in which a composite paint coat is prepared, inserted into a mold, and synthetic resin is injected.

(Publication No. 2-5 0 3 0 7 7) 0

However, this method uses volatile organic ^ PJ in the process of manufacturing the composite paint coat, so that the P problem of environmental protection has not been sufficiently solved, and several steps of coating are performed on a casting sheet. Or also casting It requires a step of peeling off the sheet, and has the disadvantage that it is complicated. In addition, this method cannot make the transparent layer, the expansion layer, and the adhesive layer sufficiently thick. Therefore, when manufacturing a molded article such as an automobile exterior member that is complicated and has a large expansion ratio due to shape, it is a final recommendation. Necessary adhesion between layers ¾Jg force <cannot be obtained ヽ There were problems such as uneven gloss and uneven color.

Disclosure of the invention

An object of the present invention is to improve the disadvantages of the prior art, eliminate the need for a coating step and eliminate the use of a casting sheet, and provide a co-extruded metal, sheet and sheet having excellent light and color. It is an object of the present invention to provide a method for producing a plastic molded product, particularly an automobile exterior member.

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the above-described objective power ¾1 ^ has been obtained by using a co-extruded multilayer ¾s sheet having a specific layer configuration and by forming this sheet. The present invention has been found.

That is, one of the present invention is a thermoplastic acrylic polymer containing a ^ agent and

A colored layer (A) composed of Z or a thermoplastic resin, an employment of a modified olefin polymer containing at least one kind of t! S selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group. A co-extruded multilayer sheet characterized in that (B) and a back-up layer (C) comprising an olefin polymer are laminated in the order of (A) / (B) / (C).

Another aspect of the present invention is to provide a colored layer (A) comprising a thermoplastic acryl-based polymer and / or a thermoplastic fluororesin containing a colorant, a carboxyl group, a hydrate group, a hydroxyl group and a glycidyl group. (B) comprising at least one modified S-containing olefin polymer selected from the group consisting of: and a backup layer comprising the olefin polymer

(C) is formed into a sheet by co-extruding female in the order of (A) / (B) / (C) to form a sheet, and the sheet is formed into a preform having a three-dimensional shape, and the preforming is performed. A method for producing a plastic molded article, comprising inserting an article into an injection molding die and then injecting an olefin polymer into contact with the backup layer (C). Here, the thermoplastic acrylic polymer and / or the thermoplastic fluororesin constituting the layer (A) is at least one kind selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group. A modified thermoplastic acryl-based polymer containing 1% of food and Z or a modified thermoplastic fluororesin are preferred in view of further increasing the durability of adhesion.

A modified thermoplastic acrylic polymer containing at least one kind of tim selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group, between the layer (A) and the layer (B); It is preferable that the layer (D) made of modified thermoplastic resin be further laminated from the viewpoint of further increasing the durability of adhesion.

Further, the fact that the transparent layer (T) made of an organic or inorganic compound having an excess ratio of 75 is further provided on the surface of the layer (A) is advantageous in that the color depth of the co-extruded multilayer シート ^ sheet surface is further increased. Is preferred.

Further, the conjugated material constituting the layer (T) is preferably a thermoplastic acrylic polymer and / or a thermoplastic fluorinated resin, and is preferred in terms of its formability.

Further, when the plastic body is an automobile exterior member, a particularly large effect can be expected.

BEST MODE FOR CARRYING OUT THE INVENTION

Each layer configuration of co-extruded multilayer laminate sheet

1. Layer (A)

The layer (A), which is one of the constituent layers of the co-extruded multilayer laminated sheet of the present invention, is a fiber blended with a coloring agent (eg, a pigment) commonly used in thermoplastic acrylic polymers and / or thermoplastic resins. It consists of Examples of the thermoplastic acrylic polymer include, for example, atarilic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, There are homopolymers such as acrylonitrile and methacrylonitrile, and copolymers containing these as main components. Specific examples include polymethyl acrylate, methyl methacrylate-methyl acrylate copolymer, and methyl methacrylate-ethyl acrylate copolymer. In addition to polymers, methyl methacrylate-ethyl methacrylate copolymer, polyacrylonitrile, acrylonitrile-methyl methacrylate copolymer, etc., as well as acrylonitrile and / or ^ or methacrylic acid ester for rubbery polymers Graft copolymers are listed in the official gazettes of Japanese Patent Publication No. 49-146, 58, 49-461, 59, 50-90 22 and 60-233 35 Impact-resistant acryl-based polymers obtained by such multi-stage polymerization can be exemplified. Above all, a homopolymer of methyl methacrylate or acrylonitrile or a copolymer containing these as components is preferable. It should be noted that these thermoplastic acrylic polymers are not excluded from being blended with other polymers such as polyvinylidene fluoride, polycarbonate, and the like, as long as the coloring properties, physical properties, and moldability are not significantly impaired. Further, two or more resins can be used in combination.

Examples of the thermoplastic resin include, for example, polyvinyl fluoride, polyvinylidene fluoride, polychloroethylene trifluorethylene, ethylene-tetrafluoroethylene copolymer, ethylene monochlorotrifluoroethylene copolymer, Commercial products such as tetrafluoroethylene-ethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene-pyrene copolymer, and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer are available. Although used appropriately, polyvinyl fluoride and polyvinylidene vinylidene are particularly preferred. It should be noted that these thermoplastic fluororesins do not exclude other polymers such as polymethyl methacrylate and additives, for example, as long as their properties and impact resistance are not significantly impaired. Also, two or more resins can be used together.

& Ru 0

Examples of colorants include azo pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, perylene pigments, perinone pigments, and dioxazines. And organic pigments such as quinophthalone pigments; and inorganic pigments such as titanium oxide, red iron oxide, ultramarine, graphite, chromium permillion, and complex oxide pigments. The amount of the colorant to be added to the thermoplastic acryl-based polymer and / or the thermoplastic resin is usually 0.1 to 20 Mfi%, preferably 0.1 to 20 Mfi%, from the viewpoint of the design property and the polymer content. 5 to 10 times; S%.

In addition, the thermoplastic acrylic polymer and Z or the thermoplastic fluororesin constituting the layer (A) may be modified in the layer (D) described below in order to further increase the durability of the adhesive strength. It is preferable to use a thermoplastic acryl-based polymer and Z or a modified thermoplastic fluororesin. The modification is carried out by a method of blending a thermoplastic polymer having compatibility with a thermoplastic acrylic polymer and / or a thermoplastic fluororesin and having a functional group. .

2. Layer (B)

The layer (B), which is one constituent layer of the co-extruded multilayer laminated sheet of the present invention, is a modified olefin polymer containing at least one functional group selected from a carboxy group, an acid anhydride group, water and a glycidyl group. It consists of Here, the homopolymer of α-olefin such as ethylene, propylene, butene, pentene, hexene, octene, decene, 3-methylbutene, 4-methylpentene, etc. In addition to the coalescing, these α-olefins are separated into blocks, random or graphitic copolymers based on other heavy monomers (for example, diolefins, unsaturated carboxylic acids are derivatives, vinyl esters, aromatic vinyls, etc.). Coalescing is preferably used. Specifically, for example, polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-3-methylbutene copolymer, ethylene-4-methylpentene copolymer, propylene-butene copolymer Polymer, ethylene-butadiene copolymer, propylene butadiene copolymer, ethylene-vinyl sulphate copolymer, ethylene-acryl An acid copolymer, an ethylene-ethyl acrylate copolymer and the like can be mentioned. Among them, crystalline resin is particularly preferable. Preferred types are an ethylene polymer resin and a propylene polymer resin. As long as the adhesion, physical properties, and moldability are not significantly impaired, it is not excluded that these olefin polymers are combined with other compatible polymers, additives, fillers, pigments, and the like. . In addition, two or more of these polymers can be used in combination.

As a method for incorporating such functional groups into such an olefin polymer,

(1) a method of subjecting a heavy monomer having a functional group and an olefin polymer to a graft reaction condition,

(2) a method of block- or random-copolymerizing a heavy monomer having a thigh and α-olefin;

(3) A method of reacting a reaction ¾S present in the polymer of an olefin with a compound having a governmental US or a compound ^^ that forms a functional group by a reaction.

(4) Method of introducing the! S by oxidation, hydrolysis, thermal decomposition, etc.

(5) a method of blending the functional group-containing olefin polymer and the olefin polymer obtained by the methods (1) to (4),

And the like. Among them, the methods (1) and (2) are most preferable because they do not impair the physical properties of the polymer.

In the methods (1) and (2), the heavy monomer having a functional group may be a carboxyl group or an acid anhydride group, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. And hymic acid (3,6-endmethylenetetrahydrophthalic acid) or their anhydrides (among them, acrylic acid and maleic anhydride are preferred in terms of adhesiveness). When the functional group is a hydroxyl group, for example, Samples of vinyl ester polymers such as vinyl acetate, vinyl polypropionate, and ethylene monoacetate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; and divalent alcohols There are unsaturated alcohol polymers and the like, in which unsaturated alcohols such as monoesters with polyesters are homopolymerized or copolymerized with other heavy monomers, and when the glycidyl group is a dalicidyl group, for example, glycidyl acrylate, glycidyl methacrylate And glycidyl ethyl acrylate, glycidyl itaconate, and the like (of which glycidyl acrylate is preferable in terms of reactivity).

In the modified olefin polymer obtained by such a method, the content of the functional group is required to be at least 0.001 mol Z 100 g from the viewpoint of adhesiveness. Physical properties such as impact strength and rigidity balance, and compatibility with the same type of unmodified resin

A force of less than 0.3 mol / 100 g is preferred, and among them, 0.05 to 0.2 mol Z 100 £, particularly 0.01 to 1 mol / ^ 100 g is preferred.

In addition, as long as ^ S of the t! S is within the above range, the modified olefin polymer contains 2 to 60 (particularly 5 to 50)% by weight of an amorphous rubbery polymer. This is preferable because the adhesiveness with the thermoplastic acryl-based polymer and / or the thermoplastic fluororesin is improved. Examples of rubbery polymers include ethylene copolymers such as ethylene-propylene copolymer rubber, ethylene-propylene-gen copolymer rubber, ethylene-butene-11 copolymer rubber, and propylene-butene-11 copolymer rubber. Although the strength of coalesced rubber and various types of rubbery polymers can be used, the olefin copolymer rubber is preferably used from the viewpoint of improving compatibility with the modified olefin polymer and adhesion. Further, the modified olefin polymer may further contain other thermoplastic polymers such as polyamides and polyesters, as long as the adhesiveness, physical properties, and the like are not significantly impaired. 3. Layer (C)

The layer (C), which is one of the constituent layers of the co-extruded multilayer laminated sheet of the present invention, is a backup layer made of an olefin polymer. Here, the olefin polymer can be appropriately selected from the olefin polymers used for modification in the above-mentioned modified olefin polymer, and among them, a crystalline resin-like one is particularly preferable. Better No. Preferred types are ethylene polymer resin and propylene polymer resin. In addition, as long as the physical properties and moldability are not significantly impaired, the addition of other polymers, additives, fillers and the like is not excluded for the olefin polymer. Further, two or more of these polymers can be used in combination.

4. Layer (D)

A carboxyl group, a hydrate group, a 7_R acid group and a glycidyl group are added between the above-mentioned layer (A) and layer (B) of the co-extruded multilayer laminated sheet of the present invention in order to further increase the durability of the adhesive strength. It is preferable to further laminate a layer (D) comprising a modified thermoplastic acryl-based polymer containing at least one member selected from the group consisting of Z and Z or a modified thermoplastic resin. Here, as the thermoplastic acrylic polymer and Z or the thermoplastic fluororesin used for the modification, the thermoplastic acryl-based polymer and / or the thermoplastic resin described as constituting the layer (A) are used. It can be used properly from among them. Among them, a polymer of methyl methacrylate or acrylonitrile or a copolymer containing these as a component, polyvinyl fluoride, or polyvinylidene fluoride is preferable. In addition, these thermoplastic acrylic polymers and fluorinated or thermoplastic fluororesins do not include other polymers or additives unless they are significantly impaired in transparency, moldability or impact resistance. do not do. Also, two or more resins can be used in combination. For example, polyvinylidene fluoride, polycarbonate, or the like can be mixed with a thermoplastic acrylic polymer, or polymethyl methacrylate or the like can be mixed with a thermoplastic resin.

As a method for modifying the thermoplastic acryl-based polymer and / or thermoplastic resin by adding the above functional group to the thermoplastic resin,

(1) A method of blending a thermoplastic polymer having compatibility with a thermoplastic acrylic polymer and / or a thermoplastic fluororesin, and having a functional group and a functional group,

(2) A heavy ^ ft monomer having a government food IS, a thermoplastic acrylic polymer and Z or A method of subjecting a thermoplastic fluororesin to graft reaction conditions,

(3) a method of block or random copolymerization of a heavy monomer having a public opinion, a heavy acrylic monomer and a monomer containing Z or heavy fluorine,

(4) a method of reacting a reaction present in a thermoplastic acryl-based polymer and / or a thermoplastic resin with a compound having a functional group or a compound having a functional group by a reaction,

(5) Method of introducing official side by oxidation, hydrolysis, thermal decomposition, etc.

Among these methods, the method (1) is the most convenient and preferable.

In the method of (1), the thermoplastic polymer having compatibility with the thermoplastic acrylic polymer and / or the thermoplastic resin and having a good quality is preferably a carboxyl group or an acid anhydride. Of acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, etc. containing at least one kind selected from the group consisting of Can be used. Specifically, for example, polyacrylic acid, polymethacrylic acid, methyl methacrylic acid-methacrylic acid ^ copolymer, methyl methacrylate-monoacrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, hydroxyethyl ethyl polyacrylate, poly Hydroxyethyl methacrylate, acrylate-hydroxyethyl acrylate copolymer, acrylate-hydroxyethyl methacrylate copolymer, methacrylate-hydroxyethyl acrylate copolymer, methyl methacrylate-hydroxyethyl methacrylate copolymer Glycidyl polyacrylate, polyglycidyl methacrylate, glycidyl acrylate / glycidyl acrylate copolymer, acrylate-glycidyl methacrylate copolymer, methyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid Examples thereof include a methyl-glycidyl methacrylate copolymer.

In the methods (2) and (3), the heavy monomer having When ¾ is a carboxyl group or an acid anhydride group, there are, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, hymic acid or anhydrides thereof (among others, acrylolic acid in terms of adhesiveness). And maleic acid are preferred). In addition, when the IS is a hydroxyl group, for example, acrylates of vinyl ester polymers such as polyvinyl vinyl succinate, polyvinyl propionate, and ethylene-vinyl acetate copolymer, and unsaturated acids such as acrylic acid and methacrylic acid An unsaturated alcohol polymer obtained by homopolymerizing an unsaturated alcohol such as a monoester of a carboxylic acid and a dihydric alcohol or copolymerizing with another heavy ft monomer is also available. When the thigh is a glycidyl group, examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethyl acrylate, and glycidyl itaconate (among them, glycidyl acrylate is preferred in terms of reactivity). Further, as the heavy acryl-based monomer, a heavy acryl-based monomer which is a unit capable of constituting a thermoplastic acryl-based polymer can be used. Further, as the deuterium-fluorine-containing monomer, a suitable one can be selected from deuterium-fluorine-containing monomers, which are units capable of constituting a thermoplastic fluororesin.

In the modified thermoplastic acrylic polymer and / or modified thermoplastic fluororesin obtained by such a method, the content of the functional group contained therein is determined from the viewpoint of adhesiveness.

0.1 g / 100 g or more is required.On the other hand, from the viewpoint of moldability, physical properties such as impact resistance—rigidity balance, and compatibility with the same type of unmodified resin, 0.3 mol / g It is preferably less than 100 g and more preferably 0.005 to 0.2 mol 100 g, particularly preferably 0.01 to 0.1 mol / 100 g.

5. Layer (T)

The transparent coating (T) which may be further provided on the surface of the above-mentioned footwear (A) of the co-extruded multilayer laminated sheet of the present invention is a layer comprising an inorganic compound having a transmittance of 75% or more. is there. Providing a transparent exhibition (cho) increases the color depth of the coextruded multi-expanded laminated sheet surface. It is preferable from the viewpoint of further addition.

Here, examples of the organic compound include thermoplastic acrylic polymer, thermoplastic fluororesin, polycarbonate, polystyrene, diethylene glycol bisarylcarbonate resin, polyvinyl chloride, acrylonitrile-styrene copolymer resin, and styrene-methyl methacrylate copolymer. In addition to polymer resin, polycyclohexyl methacrylate, poly-4-methylpentene-11, etc., JP-A-61-27308, 61-272, 216, 61 —A copolymer resin of ethylene and cyclic olefin described in each of the publications can be used. In addition, mineralization ^! For example, silica can be mentioned. As a method of laminating the inorganic compound, a method of co-extrusion of an inorganic compound and the above-mentioned polymer, which is previously melted and pelletized, and a method such as vapor deposition, sputtering, and coating are used.

Among them, ItX is a thermoplastic acryl-based polymer and / or a thermoplastic fluorinated fat among inorganic compounds in terms of thermal β-property, and in particular, a m-polymer of methyl methacrylate or acrylonitrile or these. The main copolymer, polyvinyl fluoride, and polyvinylidene fluoride are preferred. It should be noted that these thermoplastic acrylic polymers and / or thermoplastic resins are not excluded from being combined with other polymers or additives unless the transparency, moldability or impact resistance is significantly impaired. In addition, two or more resins can be used in combination. For example, polyvinylidene fluoride, polycarbonate, and the like can be blended with a thermoplastic acryl-based polymer, and polymethyl methacrylate and the like can be blended with a thermoplastic resin.

Manufacture of co-extruded multi-layer sheet

In the present invention, the above (A) z layer (B) / layer (c) and layer (A) / m (D) are formed by co-extrusion using the material constituting each layer described above. / m (B)

Z layer (C), layer (T) / layer (A) / layer (B) / layer (C) or layer (T) Z layer (A) Z layer (D) Z layer (B) / layer (C) Hired to manufacture laminated sheets. Both In extrusion molding, usually, the material constituting each layer is melted by each extruder, and each layer is successively layered using a feed block. Winding the seed layer sheet using a winder is not powerful.

When the feed block and the die's fijg are uniform, the material constituting each layer should be intense, with the melting point of the material brass lower than 80 ° C.

Regarding the thickness of each layer, the layer (A), which is a colored layer, is preferably in the range of 50 to 500 m in order to create a color required for an exterior member of an automobile, and particularly preferably 50 to 400 m. ^ m is particularly preferred. Layer (B) and layer (D) are each preferably in the range of 5 to 300 to obtain the required adhesion between the colored layer and the backup layer, and are preferably 30 to 300 m. Is particularly preferred. The layer (C) serving as the backup layer preferably has a thickness in the range of 100 to 100 zm in order to suppress breakage due to the shape of the 時 f® sheet described later and the injection pressure at the time of injection. . The layer (T) is preferably in the range of 5 to 200 in order to provide the color depth of the sheet surface required for an automobile exterior member.

The thickness of each layer of the co-extruded multilayer laminate sheet is preferably determined in consideration of the expansion ratio described later. More specifically, in the case of the shape: ^ crisp! ^ Shape, the thickness of each layer is set to be slightly thicker within the range of the thickness of each layer described above.

Spare by ^^ shape

The laminated sheet thus obtained is then formed into a preliminary 5 ^ -body having a three-dimensional shape. As the ^^ shape, a means such as a true ^^ pressure ^^, a true E2 ^^ type, etc. is preferably employed. In the case of true ^^, for example, the above-mentioned co-extrusion multi-layer sheet is used with far-infrared ceramic heaters from both sides. After heating, the mold is moved up, down, left and right, a part of the heated laminated sheet is brought into contact with the mold, and the air generated between the laminated sheet and the mold is evacuated to form a vacuum. A method in which the surface is brought into close contact with a mold, shaped, and cooled and solidified by a forced cooling method using a fan, a blower or the like is preferable. Here, the surface of the laminated sheet at the time of evacuation is in the range of 'ag: Lt lower than the melting point of the resin or polymer constituting each layer by 5 ° C and' a ° 'higher than the melting point by 5 ° C. It is preferable that

These processes include a batch process and a continuous process. In addition, a process in which heating and trimming processes are all performed at one location, and a process such as this process is performed while moving the sheet 1 by a transfer device such as a clamp. In order to obtain a good molded product, a part of the laminated sheet is brought into contact with the mold before it is brought into contact with the mold. It is preferable that a step of spraying ^ from the direction to move the mold while inflating the Ml heat sheet into a hemispherical shape and bringing "^" of the recruitment sheet into contact with the mold is added to the upper part.

Injection of olefin polymer into preform.

Next, injection is performed on a hard, high-gloss, highly polished surface that has the same shape as the preform obtained by IWing the coextruded multilayer laminated sheet as described above, and that has no surface defects. After inserting the preform into a pair of injection molding dies having the cavities, the mold is closed, and a space is formed for injecting the β-olefin polymer β in contact with the backup of the preform, This is carried out by injecting the olefin polymer into the space so as not to come into contact with the {f-side transparent film} of the backup layer. As the olefin polymer used here, a crystalline resinous material is particularly preferable because it can be appropriately selected from the olefin polymers used in the backup layer and can be used. Preferred are ethylene polymer resin and propylene polymer resin. It should be noted that, as long as the physical properties and male properties are not hindered, the olefin polymer is not required to be blended with other polymers, additives and filling power. In addition, two or more of these polymers may be used in combination.

This injection molding is carried out using a conventional injection molding machine at an i® temperature of 180 to 250, preferably 200 to 230 ° C, 100 to 2000 kg / cm ² , preferably 500 to 1500. 2 / (:. 111 takes place in the ^second emission output further more as the preform is not deviated in the injection pressure, which was inserted into a mold Kiyabiti one, the preform by vacuum suction Ya slide core such It is more preferable to fix to the mold cavity.

Difficult example)

Hereinafter, the present invention will be further described with reference to specific examples.

Evaluation method

(1) Gloss: The coextruded multi-layered laminated sheet was subjected to Hffi according to the IEK emissivity of incident light at an angle of 60 degrees in accordance with JIS-K7105.

(2) {Sit weather resistance: After exposing a sheet molded with a black panel 63 ° C sunshine carbon arc lamp type e-Zeometer (based on JIS-B 7753) for 1200 hours, the light's hue change was observed. .

(3) Adhesion: Cut the worksheet and preform into strips with a width of 10 mm, and apply them between the layer (A), which is a colored calendar, and the layer (B), which is a modified olefin polymer, or heat of modification. After peeling off a part between the layer (D), which is a thermoplastic acryl-based polymer layer and / or the layer (B), which is a modified thermoplastic fluororesin, an instrument with an in-situ tester is used. T peeling was performed at a speed of 50 mm / min.

(4) Uneven gloss: The preliminary male body was visually tfed.

(5) Color unevenness: The preliminary blank was visually evaluated.

Case example 1

(1) Each of the following materials is melted using four mi * extruders, and Each layer was successively extruded from a T-die, and formed by cooling with a forming roll composed of three polishing rolls, thereby producing a co-extruded multilayer laminated sheet having the following layer constitution. The feed block and T die at that time were 230. Set to C. (Layer structure)

The transparent layer (T), the Z colored layer (A), the modified olefin polymer layer (B), and the backup layer (C) were laminated in this order. The thickness of each layer of the obtained laminated sheet is as follows: transparent layer (T) 100 ιπκ colored layer (Α) 200 / m, modified olefin polymer layer (B) 100 jum, and knock-up layer (C) 400 / zm. there were.

Thigh)

Transparent layer (T): Polymethyl methacrylate (PMMA).

Colored layer (A): White polymethyl methacrylate (white PMMA) obtained by adding 2 parts by weight of ICI titanium oxide and trade name "RTC 30" to 100 SS parts of polymethyl methacrylate and melting at 210 ° C ). Modified olefin polymer layer (B): maleic anhydride group ^ * 0.016 mol

Maleic anhydride-modified polypyrene pyrene (MN-modified PP), 100 g, MFRl. 0 g / 10 min.

Backup layer (C): MFRO. 5 g / l 0 min polypropylene (PP).

(2) Cut the laminated sheet thus obtained to 30 cmZ 30 cm, fix it in the heating and forming zone using a vacuum forming machine manufactured by Asano Laboratories, and use a far infrared ceramic heater from both sides. After heating until the surface reached 150 to 200 ° C., the sheet was turned according to the above-mentioned straightening method, and an excess sheet portion was cut off to obtain a preform having a complicated three-dimensional shape. The typical dimensions of the vacuum J¾¾ mold were 15 cm long x 5 cm wide and 5 cm deep (average expansion ratio 3.2 times).

(3) Next, the above preform was set in the mold cavity of the injection molding machine, and in contact with the backup, the ethylene # was 8.2 SB% and the flexural modulus was 10,000 kg gZcm ² , 60 parts by weight of propylene-ethylene block copolymer with MFR of 33 g / 10 minutes, Mooney viscosity at 100 ° C ML _{1 + 4} of 70, density of 0.86 gXcm ³ A composition obtained by melting 30 parts by weight of propylene copolymer rubber and 10 parts by weight of talc having an average particle diameter of 5.Oyum or less and a specific surface area of 3.5 m ² g or less at 210 ° C is resin- ^ 210 ° C Injection injection was performed to obtain an integrated molded body (plastic part for automobile exterior) having a sheet on the outer surface. Table 1 shows the results of evaluation of this body.

Difficult case 2

Instead of the MN-modified PP used as the modified olefin polymer layer (B) in Example 1, an ethylene-glycidyl methacrylate copolymer (GMA-modified PE, MFR 1.0 min, GMA content 0.016 mol / 100 g) was used. The results of! Hffi are shown in Table 1 in the same manner as in Example 1 except that they were used.

Example 3

Instead of the MN-modified PP used as the modified olefin polymer (B) in Example 1, an ethylene-hydroxy methacrylate copolymer (HEMA-modified PE, MFR 1.0 gZl 0 min, HEMA ^ O. 020 mol / Table 1 shows the results of the evaluation performed in the same manner as in Example 1 for H¾5 except that 100 g) was used.

Example 4

In place of the white PMMA used as the felling fellow (A) in Example 1, 5 parts by weight of Daiwa Metal Powder Co., Ltd. aluminum paste, trade name "SAP771N" was added to 100 parts by weight of polymethyl methacrylate at 210 ° C. Table 1 shows the results of the evaluation performed in the same manner as in Example 1 of H 1S except that the colorless PMMA obtained by melting was used.

Example 5

(1) Each of the following materials was melted using five single-screw extruders, and Each layer was successively laminated by a plastic, extruded from a T-die, and cooled and shaped by a roll composed of three polishing rolls to produce a co-extruded multilayer laminated sheet having the following layer constitution. The feed block and T die at that time were set to 230 ° C. (Layer structure)

Transparent layer (T) Z-colored layer (A) Z-modified thermoplastic acrylic polymer layer (D) Modified olefin polymer layer (B) Z-backup layer (C). The thickness of each layer of the obtained laminated sheet is as follows: transparent layer (T) 100 / m. Colored layer (A) 200 ^ m, modified thermoplastic acrylic polymer layer (D) 100 rn, modified olefin polymer layer.

(B) 10 Oum, backup layer (C) 300 / m.

(Material)

Transparent layer (T): Polymethyl methacrylate (PMMA)

Colored layer (A): White polymethyl methacrylate (white) obtained by adding 2SS parts of ICI titanium oxide, trade name "RTC 30" to 100 parts by weight of polymethyl methacrylate and melting at 210 ° C PMMA) o Modified thermoplastic acrylic polymer (D): 80 parts by weight of poly (methyl methacrylate) and a copolymer of methyl methacrylate and glycidyl methacrylate

(MMA-GMA copolymer GMA ^ ftO. 35mol / ^/ 1008)

GMA-modified polymethyl methacrylate (GMA-modified PMMA) obtained by melting 20 parts by weight at 210 ° C.

Modified olefin polymer layer (B): maleic anhydride group 1: 0.016 mol Z

100 g MFR 1.0 g / 10 min maleic anhydride-modified polypropylene (MN-modified PP) o

Back-up layer (C) MFR 0.5 g / 10 min polypropylene (PP) The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Difficult case 6 Instead of the GMA-modified PMMA used as the modified thermoplastic acrylic polymer layer (D) in Example 5, 80SS part of polymethyl methacrylate and methyl methacrylate hydroxyethyl methacrylate copolymer (MMA-HEMA copolymer,

HEMA S0. 30 mol 1002) Table 1 shows the results of evaluation in the same manner as in Example 5, except that 重量 modified PMMA obtained by melting 20 parts by weight at 210 ° C was used.

H½Example 7

Instead of the GMA-modified PMMA used as the modified thermoplastic acrylic polymer layer (D) in Example 5, 80 parts by weight of polymethyl methacrylate and methyl methacrylate-methacrylic acid copolymer (MMA-MAA copolymer, MAA ^ SO. 37 mol / 100 g) Table 1 shows the results obtained in the same manner as in Example 5 except that MMA-modified PMMA obtained by melting 20 parts by weight at 210 ° C was used.

Difficult case 8

(1) Each of the following materials is melted using four extruders, and each layer is successively spread by a feed block, extruded from a T-die, and consists of three polishing rolls] ^ A co-extruded multilayer sheet having the following layer structure was formed by cooling and shaping with a roll. At that time, '^' of the feed block and T die was set to 230 ° C.

(Story S 構)

The transparent layer (Τ) / colored layer (Α) -modified modified polymer layer (Β) / backup layer (C) were laminated in this order. The thickness of each layer of the obtained laminated sheet was 100 um for the transparent layer (Τ), 200 m for the colored layer (A), 100 m for the modified olefin polymer layer (B), and 400 um for the knock-up layer (C).

Picture 3

Transparent layer (T): Polymethyl methacrylate (PMMA).

Wear feS (A): Polymethyl methacrylate 80 parts by weight of methyl methacrylate Addition of 20 parts by weight of glycidyl acrylate copolymer (MMA-GMA copolymer, GMA ^ iO. 35 mol / "100 g") and 2 parts by weight of ICI titanium oxide, trade name "RTC 30" White GMA-modified polymethacrylate (white GMA-modified PMMA) obtained by melting at 210 ° C.

Modified olefin polymer layer (B): maleic anhydride group S 0.016 mol /

Maleic anhydride-modified polypropylene (MN-modified PP), 100 g, MFRl. Og / 10 min.

Backup layer (C): Polypropylene (PP) of 0.5 gZl 0 min. Hereinafter, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 9

In place of white GMA modified 着色 used as coloring agent (Α) in Example 8 80 SS part of poly (methyl methacrylate) and a copolymer of methyl methacrylate-hydroxechinole methacrylate (ΜΜΑ- ΗΕΜΑ copolymer ^ HEMA ^ gO. 30 mol Zl 00g) Evaluation results in the same manner as in Example 8 except that 20 SS part and IC I¾h titanium oxide, 2 parts by weight of trade name “RTC30” were added and white HEMA-modified PMMA obtained by melting at 210 was used. Are shown in Table 1.

Example 10

Instead of the white GMA-modified PMMA used as the colored layer (A) in Example 8, polymethyl methacrylate 80 SS part and methyl methacrylate-methacryl ^ polymer (MMA-MAA copolymer, MAA ^ SO. 37 Morno 100 £ ) In the same manner as in Example 8, except that 20 parts by weight and 2% by mass of titanium oxide manufactured by ICI, trade name "RTC 30" were added and melted at 210 ° C to obtain a white MAA-modified PMMA. Table 1 shows the results of fHffi.

«Example 11 (l) Each of the following materials is melted using three m $ extruders, and each layer is sequentially extruded by a feed block, extruded from a T-die, and formed by a forming roll consisting of three polishing rolls. By cooling and shaping, a co-extruded multilayer laminated sheet having the following layer constitution was prepared. At that time, the temperature of the feed block and the T-die was set to 230 ° C. (Layer structure)

The colored layer (A) / modified olefin polymer was employed (B) and the Z-packed layer (C) was laminated in this order. The thickness of each layer of the obtained laminated sheet was 200 μm / m for the feather (A) and 100 m for the modified olefin polymer layer (B) and 500 m for the backup layer (C).

(Material)

Colored layer (A): White poly (methyl methacrylate) obtained by adding 2 MS parts of ICI's titanium oxide (trade name: RTC30) to 100 parts by weight of poly (methyl methacrylate) and melting at 210 ° C ( White PMMA). Modified olefin polymer 曆 (B): maleic anhydride group ^ SO. 016 mol /

100 g, MFRl. 0 gZl 0 min. Maleic anhydride-associated polypropylene (MN-modified PP).

Knockup layer (H: polypropylene (PP) with MFR of 0.5 gZl 0 min.) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Difficult case 12

(1) Each of the following materials is melted using three mt-type extruders, each layer is sequentially employed by a feed block, extruded from a T die, and cooled by a roll composed of three polishing rolls. A co-extruded multilayer sheet having the following layer configuration was formed. At that time, the feed block and T die were set at 230 ° C. C (Layer composition)

^ M (A) Z-modified olefin polymer layer (B) Z backup layer (C) Laminated. The thickness of each layer of the obtained laminated sheet was a colored layer (A) 200 / m, a modified olefin polymer layer (B) 10 and a backup layer (C) 500 111.

Original)

Colored layer (A): Polymethyl methacrylate 80 weight parts and methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GMA ^ SO. 35 mol / 100 g) 20 M parts and ICI Ne ± S¾ Titanium oxide, 2 parts by weight of trade name “RTC30” added and melted at 210 ° C, white GMA-modified polymethyl methacrylate (white GMA-modified PMMA)

Modified olefin polymer layer (B): maleic anhydride group S 0.016 mol

100 g MFRl. Og / 10 min anhydrous maleic S ^ -polypropylene (MN-modified PP).

Backup layer (C) MFRO. 5 g / l 0 min polypropylene (PP) The evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

H. The results were evaluated in the same manner as in Example 1 except that in place of the MN-modified PP used as the modified olefin polymer layer (B) in Example 1, an unmodified polyethylene (PE) of MFR 1.0 gZl 0 min was used. See Table 1.

Difficult case 13

Table 2 shows the results of the evaluation performed in the same manner as in Example 1 except that the following materials were used instead of the layered materials used in Example 1.

(Material)

Transparent layer (T): polyvinylidene fluoride (PVDF).

Colored layer (A): Titanium oxide manufactured by ICI, White polyvinylidene fluoride (white PVDF) obtained by adding 2 SS part of the product name “RTC 30” and melting at 210 ° C.

Modified olefin polymer layer (B): maleic anhydride group ^ SO. 016 mol Z

100 g. MFR 1.0 g / 10 min maleic anhydride-modified polypropylene (MN-modified PP).

Backup layer (C): MFR 0.5 gZl 0 min polypropylene (PP).

Example 14

Instead of the MN-modified PP used as the modified olefin polymer (B) in Example 13 of HJfe, an ethylene-glycidyl methacrylate copolymer (GMA-modified PE, MFR 1.0 gZl 0 min, GMA ^ JiO. 016 mol / 100 g Table 2 shows the results of the evaluation performed in the same manner as in Example 13 except that) was used.

In place of the MN-modified PP used as the modified olefin polymer layer (B) in Example 13, an ethylene-hydroxyethyl methacrylate copolymer (HEMA-modified PE, MFR 1.0 gZl 0 min, HEMA S.020 mol / 100 g) Table 2 shows the results obtained in the same manner as in Example 13 except for using.

H¾Example 16

代わり In place of the white PVDF used as the colored layer (Α) in Example 13, 100 parts by weight of polyvinylidene fluoride was added with 5 parts by weight of Daiwa Metal Powder Industrial: tSi aluminum paste, trade name “SAP771N”. Table 2 shows the results of the evaluation performed in the same manner as in Example 13 except that the metallic PVDF obtained by melting at 210 ° C was used.

Example 17

H. Table 2 shows the results obtained in the same manner as in Example 5 except that the composition of the co-extruded multilayer laminated sheet prepared in Example 5 and the materials constituting the layers were changed as follows. (Layer structure)

The transparent layer (T) / colored layer (A) modified thermoplastic fluororesin layer (D) / modified olefin polymer layer (B) and Z backup layer (C) were laminated in this order. The thickness of each layer in the obtained laminated sheet is 100 m for the transparent layer (T), 20 O ^ m for the colored layer (A), 100 nm for the modified thermoplastic resin layer (D), 100 nm for the modified olefin polymer layer (B). ) 100 μπι, Knock-up layer (C) 300 m.

Recitation)

Transparent layer (T): polyvinylidene fluoride (PVDF :).

Wear feS (A): White polyvinylidene fluoride obtained by adding 2 SS parts of titanium oxide manufactured by IC 1 company and “RTC 30” to 100 parts by weight of polyvinylidene fluoride and melting at 210 ° C. (White PVDF) Modified thermoplastic fluororesin layer (D): Polyvinylidene fluoride 80S * part and methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GMA ^ SO. 35mol / 100g) 2) GMA-modified polyvinylidene fluoride (GMA-modified PVDF) obtained by melting 2 OfiJt part at 210 ° C

Modified olefin polymer layer (B): maleic anhydride group ^ 0.016 mol Z

100 g MFR 1.0 gZl 0 min maleic anhydride-modified polypropylene (MN-modified PP).

Backup layer (C): MFR 0.5 g 10 minutes polypropylene (PP).

H¾S example 18

Hi In Example 17, instead of the GMA-modified PVDF used as the modified thermoplastic resin layer (D), 80 parts by weight of polyvinylidene fluoride and a copolymer of methyl methacrylate-hydroxyethyl methacrylate (including MMA-HEMA copolymer and HEMA) (0.30 mol / 100 g) 2 Obtained by fusing the OSS part at 210 ° C. Table 2 shows the results of the evaluation performed in the same manner as in Example 17 except that HEMA-modified PVDF was used.

Example 19

In Example 17, 80 parts by weight of polyvinylidene fluoride and methyl methacrylate-methacrylic acid copolymer (MMA-MAA copolymer) were used instead of the GMA-modified PVDF used as the modified thermoplastic fluororesin layer (D) in Example 17. MAA fiO. 37 mol 100 g) 2 Table 2 shows the results of iHffi in the same manner as in Example 17 except that MAA-modified PVDF obtained by melting the Offlt portion at 210 ° C was used.

H¾Example 20

Table 2 shows the results obtained in the same manner as in Example 8 except that the material of the layer configuration used in Example 8 was changed to the following material.

(Material)

Transparent (T): Polyvinylidene fluoride (PVDF).

M (A): Polyvinylidene fluoride 8 Ofifi part and methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GMA S0.35 mol 1008) 20 parts by weight and ICI material: tS titanium oxide, White GMA-modified polyvinylidene fluoride (white GMA-modified PVDF) obtained by adding 2 parts by weight of trade name “RTC30” and melting at 210 ° C.

Modified olefin polymer layer (B): maleic anhydride group * 0.016 mol /

Backup hire (C): MFR 0.5 gZl 0 min polypropylene (PP).

Example 21

Instead of the white GMA-modified PVDF used as colored layer (A) in Example 20 80 parts by weight of polyvinylidene fluoride and 20 parts by weight of methyl methacrylate monohydric methacrylate kissil copolymer (MMA-HEMA copolymer, HEMA content 0.30 mol / 100 g) and titanium oxide manufactured by ICI Table 2 shows the results of the evaluation performed in the same manner as in Example 20, except that 2 parts by weight of the trade name “RTC30” was added and the white HEMA-modified PVDF obtained by melting at 210 ° C. was used.

Example 22

Instead of the white GMA-modified PVDF used as the dressing fe ^ (A) in Example 20, 80 parts by weight of polyvinylidene fluoride and a methyl methacrylate-methacrylonitrile polymer (MMA-MAA copolymer, MAA ^ iO 37 mol / 100 g) except for using 20 parts by weight and white MAA-modified PVDF obtained by adding 2 SS parts of titanium oxide (trade name: RTC30) manufactured by ICI and melting at 210 ° C ^ Table 2 shows the results of the evaluation performed in the same manner as 8.

Example 23

Table 2 shows the results of the evaluation performed in the same manner as in Example 11 except that the layered material used in HJfe Example 11 was changed to the following material.

(Material)

Coating (A): White polyvinylidene fluoride obtained by adding 2 parts by weight of titanium oxide, trade name "RTC 30" manufactured by ICI to 100 parts by weight of polyvinylidene fluoride and melting at 210 ° C. (White PVDF). Modified olefin polymer layer (B): maleic anhydride group ^ 1: 0.016 mol

100 g, MFRl. 0 gZl 0 min anhydrous maleic i-modified polypropylene (MN-modified PP) o

Backup layer (C): MFR 0.5 g / 10 min polypropylene (PP). Difficult case 24

Example 12 except that the material of the layer constitution used in Example 12 was changed to the following material Table 2 shows the results of the evaluation performed in the same manner as described above.

(Material)

Colored layer (A): 80 parts by weight of polyvinylidene fluoride and 20 parts by weight of methyl methacrylate-glycidyl methacrylate copolymer (MMA-GMA copolymer, GA S0.35 mol 1008) and titanium oxide manufactured by ICI White GMA-modified polyvinylidene fluoride (white GMA-modified PVDF) obtained by adding 2 parts by weight of tin and trade name “RTC30” and melting at 210 ° C.

Modified olefin polymer layer (B): maleic anhydride group S. 0.016 mol /

Maleic anhydride polypropylene (MN modified PP) 100 g, MFRl. 0 gZl 0 min.

Backup layer (C): MFR 0.5 gZl 0 min polypropylene (PP). Comparative Example 2

The results were evaluated in the same manner as in Example 13 except that in place of the MN-modified PP used as the modified olefin polymer layer (B) in Example 13, unmodified polyethylene (PE) with MFR of 1.0 gZl 0 min was used. See Table 2.

Example 1 2 3 4 5 6 7 8 9 10 11 12

Example 1

[Multilayer co-extrusion multilayer lamination net]

33 A. A. A A A A A A A A A A A A B A B A B A B A B

D) ― One G H I

Modified BE Orefinoe off 曆 CB J K L J J J J J J J J J M Hack-up layer (C) N N N N N N N N N N N N 丄, Injection molded olefin polymer 0 0 0 0 0 0 0 0 0 0 0 0 0

LffTiuIIJ

T -UUijff? FR D Π U ^β —fi U n U * No 9Όί (91 92 90 91 91 92 92 91 91 92 91 91 91 Accelerated weathering

Gloss retention% 99 100 98 99 99 98 99 99 98 98 93 98 98 Hue change Δ E 0.33 0.35 0.35 0.32 0.36 0.34 0.33 0.30 0.35 0.3T 0.35 0.35 0.35 Adhesion gZl Omm

Laminated sheet 1720 1590 1600 1680 1820 1620 1580 1670 1700 1650 1550 1550 80 Preform 1T00 1610 1630 1650 3430 3120 3260 2950 3110 1610 3170 50 Uneven glossiness None None None None None None None None None None None Presence No No No No No No No No No No No No No No Note) A: PMMA B: White PMMA C: Metallic PMMA D: White GMA modified PMMA E: White H EMA modified PMM AF: White MAA modified PMMA G: GMA Modified PMMA H: HEMA modified PMMA I: MAA modified PMMA

]: ^ 1 ^ denaturation? ? ! : 01 ^ 1 eight denaturation? £: ^ 1 £ 1 ^ 1 eight denaturation? £ M: PEN: PP 0: P?% MtM

Table 2

Note) a: PVDF b: White PVDF c: Metallic color PVDF d: GMA modified PVDF e: HEMA modified PVDF f: MAA modified PVDF g: White GMA modified PVDF h: White H EMA modified P VD F i: White MA A modified PVDF '': ^ 1 ^ denature? ? 1 ^: 0 \ 1 eight modified 1 ³ £ 1: HEMA modified PE m: PE n: PP o: PP genuine

Comparative Example 3

First step:

First, the following transparent layer material was applied to a 50 m thick polyester film with good surface gloss using a reverse roll coater, and three heating plates each having a length of about 12 cm were used. By passing a multi-zone impinging air drying oven consisting of zones at a rate of approximately 7.5 mZ, the gas contained in the transparent layer material is removed, and a uniform transparent phase with a thickness of approximately 20 m is formed on the polyester film. Formed. '^ Of the three heating zones were, respectively, zone 1: 125 ° C, zone 2: 165 ° C, and zone 3: 200 ° C.

Next, the following coloring layer material is applied on the dried transparent layer using a reverse roll coater, and ^ PJ gas is removed by the same method as for the transparent layer to obtain a uniform coloring with a thickness of about 20 βm. A layer was formed on the transparent layer.

Next, apply the following adhesive material to the dried material using a reverse roll coater, and remove the gas in the same manner as for the transparent layer to form a uniform adhesive layer with a thickness of about 2.5 m. Formed on the layer.

By the above method, a film having a multilayer structure composed of the transparent layer, the layer, and the adhesive layer was formed on the polyester film.

Further, this film and a thermoplastic olefin-based elastomer sheet having a thickness of 500 m, which is a backing layer material described below, were laminated at a speed of 5 m / min. The roll temperature at that time was about 177 ° C., and the linear pressure per cm was 54 kg.

In this 5 ^ laminate, the transparent extension formed on the polyester film

The laminated structure of the / adhesive feiiZ adhesive layer was peeled off from the polyester film to obtain a multilayer laminated sheet having the following layer constitution.

(Story structure Transparent layer 20 μmZ coloring exhibition 20 m / adhesive layer 2.5 β mZ backup layer 500 (1 m

(Transparent layer material)

Component Weight parts

Methylethylketone 40.85

Petilolactone 40.85

Polymethyl methacrylate (PMMA) 6.22

UV absorber (Tinuvin 900) 0.35

Hindamine Koyasu ^ J 0.18

Polyfutsudani vinylidene (PVDF) 11.15 Solid components were added to methylethyl ketone and ptyrrolactone while mixing to dissolve the solid components. This solution contained a solid resin consisting of about 65% by weight of PVDF and about 35% by weight of PMMA.

Layer material)

Component Weight parts

Cyclohexane 9.27

Diisobutyl ketone 18.54

Petit lactone 8.34

PMMA 10. 02

P VDF 24. 04

Petit loractone 14.14

Carbon black 4.00 The coloring layer material was cyclohexane, di-methyl, which was first heated to about 55 ° C with PMMA. After being gradually mixed and dissolved in a solvent of sobutyl ketone and butyrolactone, and then cooled, PVDF was added to this mixture to prepare a state in which the PVDF was strongly dispersed in the PMMA mixed solution. Further, a black color was added to the mixed solution as black ^ S to prepare a black colored layer material. The amount of the pigment contained in this mixed solution was about 4.5% on a heavy S basis. This mixed solution contained a solid resin component consisting of about 651% PVDF and about 35% by weight of PMMA. (Adhesive layer material)

The adhesive layer material used was a chlorinated polypropylene solution (trade name: Hard Len 17LJ, toluene solution containing 30% by weight of chlorinated polypropylene having a chlorination rate of 35% by weight as a solid) manufactured by Toyo Bfil Inc.

(Backup layer material)

The knock-up material is a 500 m thick thermoplastic elastomeric elastomer (Mitsubishi Kasho “Thermolan 2510 B”) with a flexural modulus of about 5,200 kgZcm ² and an MFR of 1. OgZIO). Was used.

Second step:

The thus obtained laminated sheet is cut into a size of 30 cm x 30 cm, and fixed to the thigh zone using a machine manufactured by Asano Laboratory: ¾Shin¾ ^ machine, and the surface is 表面 Jg from both sides using a far-infrared ceramic heater. After heating to 150 to 200 ° C., vacuum forming was performed in accordance with the above-described vacuum forming method, and excess sheet portions were cut off to obtain a preform having a balanced three-dimensional shape. The typical dimensions of the vacuum mold used were 15 cm long x 15 cm wide and 5 cm deep (average expansion ratio 3.2 times).

Third step:

The above preform was set in the mold cavity of the injection machine, and in contact with the backing layer, 8.2% by weight of ethylene ^ fi, 10,000 kg / cm ^{2 of} flexural modulus, and MFR of 33 g / 10 min propylene-ethylene block copolymer Ethylene-propylene copolymer rubber with a viscosity of ML _{1 + 4} of 70, density of 0.86 g / cm ³ at 60ftt part, 100 ° C 30 weight:! Part and talc having an average particle size of 5.0 / im or less and a specific surface area of 3.5 m ² / g or less are melted at 210 ° C and injected at a resin temperature of 210 ° C. As a result, an integrated molded article (plastic part for automobile exterior) having a laminated sheet on the outer surface was obtained. Table 3 shows the results of evaluation of this body.

Comparative example 4

In Comparative Example 3, in place of the thermoplastic elastomeric elastomer sheet used as a backing material, polypropylene having a flexural modulus of 11,000 kg / cm ² and an MFR of 0.5 gZl 0 minutes (Mitsubishi Chemical Corporation) Table 3 shows the results of Hffi in the same manner as in Comparative Example 3 except that a 500 / m-thick sheet coated with “Mitsubishi Boripro EC9 J”) was used.

Table 3

Comparative Example 3 4

[Evaluation]

Gloss (60. -60.)% 91 90

Thigh weather resistance

Gloss ^ f rate 97 97

Hue change E 0.35 0.36

Dense # ¾ g / 1 Omm

Transformed sheet 870 910

Preliminary body 110 100

Gloss unevenness Yes Yes

Color unevenness Yes Yes Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, in the manufacturing method of a plastic molding, especially the manufacturing method of an automobile exterior member, the coating process of a coating material and the use of a casting sheet can be omitted. It is possible to adopt a simple process without using a car, and to have a three-dimensional shape, such as bumpers, side moldings, mudguards, wheel caps, spoilers, etc. Application to iiit is expected to be large.

Further, the present invention can be expected to be applied not only to exterior members of automobiles but also to, for example, household articles and body parts.

Claims

The scope of the claims

1. At least one member selected from the group consisting of S (A), a carboxyl group, a physical group, a hydroxyl group and a glycidyl group, which is made of a thermoplastic acryl-based polymer containing a colorant and / or a thermoplastic fluororesin. (B) consisting of a modified orefin polymer containing a polyolefin and a backup layer consisting of an orefin polymer (C). It is characterized by being laminated on jlllf of (A) / (B) / (C). Co-extrusion multi-layer jig layer ho

2. The thermoplastic acryl-based polymer and Z or the thermoplastic resin constituting the layer (A) contain at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group. The sheet according to claim 1, wherein the sheet is a modified thermoplastic acryl-based polymer and Z or a modified thermoplastic resin.

3. 餍 (A) has a thickness of 50 to 500 m, layer (B) has a thickness of 5 to 300 jtz m, and layer (C) has a thickness of 100 to 100 m; The sheet according to claim 1, wherein the sheet is:

4. Between the hire (A) and the layer (B), a modified thermoplastic acrylic polymer containing at least one type of government-owned IS selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group and a glycidyl group; The sheet according to any one of claims 1 to 3, further comprising a laminate (D) made of a modified thermoplastic resin.

5. The sheet according to claim 4, wherein the layer (D) has a thickness of 5 to 300 m.

6. The transparent layer (T) comprising an inorganic compound wherein X is an inorganic compound having a ^^ ratio of 75 on the surface of the layer (A) is further provided. Sheet.

7. The sheet according to claim 6, wherein the organic compound constituting the layer (T) is strong and is a thermoplastic acryl-based polymer and Z or a thermoplastic resin.

8. A sheet according to claim 6 or 7, wherein the layer (T) has a thickness of between 5 and 20 µm.

9. Colored layer made of thermoplastic acrylic polymer and / or thermoplastic fluororesin containing colorant (Α), at least one type of function selected from the group consisting of carboxyl group, acid anhydride group, hydroxyl group and glycidyl group The layer (変性) composed of the modified olefin polymer containing a group and the backup layer (C) composed of the olefin polymer are formed by multilayer coextrusion in the order of (Α) / (Β) / (C). After forming the preform into a three-dimensional shape by inserting the preform into an injection mold, the preform is brought into contact with the backup layer (C) to form an olefin polymer. A method for producing a plastic body, characterized by injecting β.

10. The thermoplastic acryl-based polymer and Ζ or the thermoplastic fluororesin constituting the layer (Α) are at least one kind selected from the group consisting of a carboxyl group, a medical water group, a hydroxyl group and a glycidyl group. 10. The method according to claim 9, which is a modified thermoplastic acryl-based polymer containing Z and a modified thermoplastic fluororesin.

1 1. The layer (A) has a thickness of 50 to 500 μπι, the layer (5) has a thickness of 5 to 300 μπι, and the layer (C) has a thickness of 100 to 100 μ / The method according to claim 9 or 10, wherein the thickness is zm.

1 2. Between layer (A) and layer (B), a modified thermoplastic acrylic resin containing at least one kind selected from the group consisting of carboxyl group, acid anhydride group, hydroxyl group and glycidyl group. The method according to any one of claims 9 to 11, further comprising: (D) comprising a polymer and Z or a modified thermoplastic fluororesin.

13. The method according to claim 12, wherein layer (D) has a thickness of 5 to 300 m.

14. The transparent layer (T) made of an organic or inorganic compound having a (light) ^ i ratio of 75% or more is further provided on the surface of the layer (A). The method described in.

15. The method according to claim 14, wherein the organic compound constituting the layer (T) is a thermoplastic acryl-based polymer and a thermoplastic resin.

16. The method of claim 14 or 15, wherein the hiring is between 5 and 200 / zm thick.

17. The method according to any one of claims 9 to 16, wherein the plastic molded body is an automobile exterior member.