JP4437329B2 - Method for producing laminated sheet for molding - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a molding laminated sheet having a specular metallic luster design, and particularly to a molding laminated sheet useful for automobile-related members, building material members, home appliances and the like.

  In general, when a colored resin molded member is manufactured, there are a method of kneading a pigment into the resin itself, coloring it and performing injection molding, and a method of performing spray coating after molding. In particular, when a mirror-like metallic luster design is required, the coating method is often employed rather than the coloring method because of the difficulty of kneading the pigment and the tendency of the pigment flow to be noticeable. In the case of the coating method, if the coating film is baked and crosslinked, the effect of surface protection can be expected. However, since current paints mainly use volatile organic solvents, there is no solvent such as using water-based paints or powder paints from the viewpoint of protecting the working environment against discharge of volatile organic solvents and protecting the external environment. However, at present, it is difficult to express the design of mirror-like metallic luster. On the other hand, a method has been introduced in which a colored sheet on which a moldable support resin layer is laminated instead of using a paint is integrally molded during injection molding. According to this method, a resin molded member having a mirror-like metallic luster can be produced without a solvent.

  As a sheet having a mirror-like metallic luster, a laminated sheet obtained by dry laminating a polyethylene terephthalate film, a polypropylene film or the like on which aluminum is deposited is known. In addition, a laminated sheet having a layer made of a cured film of a paint having an acrylate emulsion containing aluminum particles having a scaly and smooth surface is described (see, for example, Patent Document 1).

  However, these sheets have a mirror-like metallic luster as a flat surface, but because the vapor deposition surface is not sufficiently stretchable, cracks and gloss when subjected to molding such as vacuum molding or in-mold molding. The design of the mirror-like metallic luster was insufficiently maintained, such as causing unevenness.

  It has also been proposed to use a laminated sheet having a cured film of ink in which metal thin film strips are dispersed in a binder resin varnish (see, for example, Patent Document 2). According to this method, the stretchability can be improved, but the gloss is inferior to that of an aluminum vapor-deposited film and the like, and the gloss is further lowered during vacuum forming, resulting in uneven gloss.

JP-A-5-111991 JP 2002-46230 A

  The problem of the present invention is that a transparent or translucent thermoplastic resin film layer, a metal thin film strip and a decorative layer containing a binder resin are laminated in this order, have a mirror-like metallic luster, and are molded. Is to provide a laminated sheet for molding which can maintain good design properties with little reduction in gloss. In particular, it has a mirror-like metallic luster even when a film with low solvent resistance to the solvent contained in the high gloss ink used to form a decorative layer such as an acrylic film or polycarbonate film is used for the surface layer. And it is providing the lamination sheet for shaping | molding which can maintain favorable design property with little fall of gloss even if it shape | molds.

  In order to solve the above-mentioned problems, as a result of investigation, as a solvent for a high-gloss ink used as a dry film to form a decorative layer, the solubility of the binder resin and a transparent or translucent thermoplastic resin film layer By adopting a mixed solvent having a specific composition in consideration of the balance between swelling and deterioration, the above-mentioned problems have been solved and the present invention has been achieved.

That is, the present invention is a laminated sheet for molding having a transparent or translucent thermoplastic resin film layer and a decorative layer having a specular metallic luster, wherein the decorative layer is a metal thin film thin film as a pigment component. A binder resin as a binder component, an organic solvent having a solubility parameter of 8.6 (cal / ml) ^(1/2) or less as a solvent component, and lower monoalcohols having 1 to 5 carbon atoms. Drying of high-gloss ink containing a mixed solvent containing 50% by mass or more of one or more selected alcohols and having a solubility parameter of 8.6 to 10.3 (cal / ml) ^(1/2) Provided is a laminated sheet for molding, which is a decorative layer comprising a coating layer.

  By the above means, it is possible to provide a molding laminated sheet which has a mirror-like metallic luster and gives a design property having a good mirror-like metallic luster even after stretching by 200% by a heating vacuum forming method.

  The laminated sheet for molding provided by the present invention is a laminated sheet for molding in which a decorative layer having a metal thin film strip and a binder resin is laminated on a transparent or translucent thermoplastic resin film. Moreover, you may have the synthetic resin film layer for shaping | molding further on the above-mentioned decoration layer side. The embodiment will be described below.

(Transparent or translucent thermoplastic film)
As the transparent or translucent thermoplastic resin film used for the laminated sheet for molding of the present invention, a transparent or translucent single layer or multilayer film that is stretchable by heating is used. The film may contain a colorant.

  The transparent or translucent thermoplastic film described above is preferably a film mainly composed of a thermoplastic resin having a softening point in the range of 60 to 300 ° C. in order to perform a molding process by heat such as vacuum molding. In particular, it tends to swell in common ink solvents, but it is particularly useful when using films made of acrylic resins that excel in transparency, weather resistance, surface smoothness, and ability to be molded at relatively low temperatures. Demonstrate the effect.

(High gloss ink)
The high-gloss ink used for the decorative layer of the laminated sheet for molding of the present invention is a high-gloss ink having a mirror-like metallic luster in which metal thin film strips are dispersed in a binder resin varnish. Content with respect to the non volatile matter in the ink of a metal thin film strip is the range of 10-60 mass%. Metal powder is used for ordinary metallic inks, but when thin metal strips are used, the thin metal strips are oriented parallel to the surface of the object when the ink is printed or applied. As a result, a mirror-like metallic luster that cannot be obtained with conventional metal powder is obtained.

(Metal thin film strip)
Aluminum, gold, silver, copper, brass, titanium, chrome, nickel, nickel chrome, stainless steel, etc. can be used as the metal of the metal thin film strip used in the high gloss ink used in the decorative layer. As a method for forming a metal into a thin film, in the case of a metal having a low melting point, such as aluminum, vapor deposition, spreading if it has malleability such as gold, silver, copper, in the case of a metal having a high melting point and no malleability, Sputtering etc. can be mentioned. Among these, the metal thin film strip obtained from the vapor deposition metal thin film is preferably used. The thickness of the metal thin film is preferably 0.01 to 0.1 μm, more preferably 0.02 to 0.08 μm. The particle size of the metal thin film pieces dispersed in the high gloss ink is preferably 5 to 25 μm, more preferably 10 to 15 μm. When the particle size is less than 5 μm, the brightness of the coating film becomes insufficient. When the particle diameter exceeds 25 μm, the metal thin film strips are difficult to be oriented and the brightness is lowered, and high brightness ink is printed by a gravure method or a screen printing method. Or, when it is applied, it may cause clogging of the plate.

  In the following, a method for producing a metal thin film strip will be described using a particularly preferred vapor deposition method as an example. A polyolefin film, a polyester film, etc. can be used for the support body film which vapor-deposits a metal. First, a release layer is provided on the support film by coating, and then a metal is deposited on the release layer so as to have a predetermined thickness. A top coat layer is applied to the surface of the deposited film to prevent oxidation. The same coating agent for forming the release layer and the top coat layer can be used.

  Resin used for a peeling layer or a topcoat layer is not specifically limited. Specific examples include cellulose derivatives, acrylic resins, vinyl resins, polyamides, polyesters, EVA resins, chlorinated polypropylene, chlorinated EVA resins, petroleum resins, and the like. Solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, esters such as ethyl acetate and propyl acetate, methanol, ethanol and isopropyl alcohol. Alcohols, ketones such as acetone and methyl ethyl ketone, and alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether can be used.

  The metal vapor-deposited film is immersed in a solvent that dissolves the release layer and the topcoat layer and stirred. After the metal vapor-deposited film is peeled from the support film, the metal vapor-deposited film is further stirred to reduce the particle size of the metal thin film strips Set to 5 to 25 μm, filter and dry. The solvent is not particularly limited except that it dissolves the resin used for the release layer or the topcoat layer. Even when the metal thin film is formed by sputtering, the metal thin film can be formed by the same method as described above. When using a metal foil, it may be pulverized to a predetermined size with a stirrer as it is in a solvent.

  The metal thin film strip is preferably subjected to a surface treatment in order to enhance dispersibility in high brightness. Examples of the surface treatment agent include organic fatty acids such as stearic acid, oleic acid, and palmitic acid, and cellulose derivatives such as methylsilyl isocyanate, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, and ethyl cellulose.

(Binder resin)
As the binder resin used for the high-gloss ink used in the decoration layer, conventional gravure inks, flexo inks, screen inks, or resins usually used for paints can be used. Specifically, for example, acrylic resin for paint, vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinyl acetate resin, ethylene-vinyl acetate resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, or paint Polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, petroleum resin, cellulose derivative resin and the like are preferably used.

  In addition, in order to further improve the adhesion between the binder resin and the metal thin film strip and to prevent agglomeration and peeling of the dry film layer of the high-brightness ink forming the decorative layer, the binder resin includes a carboxyl group and a phosphate group. A resin having at least one group selected from sulfonic acid groups and metal salts thereof and amino groups can be used. The resin preferably has about 50 to 500 mmol / kg of these groups, and more preferably about 50 to 250 mmol / kg. Specifically, for example, acrylic resins for paints, vinyl chloride resins, vinylidene chloride resins, vinyl chloride-vinyl acetate resins, ethylene-vinyl acetate resins, polyolefin resins, chlorinated olefin resins, ethylene-acrylic resins, and other polymer resins. (Meth) acrylic acid, maleic anhydride, fumaric acid and / or salt thereof, (meth) acryloyloxyethylsulfonyl sodium salt, dimethylaminopropyl (meth) acrylic acid ester, etc. as copolymerization components during polymerization Or as a co-condensation component during condensation of a condensation resin such as a polyurethane resin for paint (amide-modified, urea-modified, epoxy-modified) or polyester resin (may be amide-modified, urea-modified, epoxy-modified) , Polyol component, part of polycarboxylic acid component, 2,2-di Those using tyrolpropionic acid, phthalic acid having a sulfonic acid group, diethanolaminoethyl diisopropyl phosphate ester, etc .; petroleum resins, epoxy resins, cellulose derivative resins, etc. were modified with chloroacetic acid, bromoacetic acid, concentrated sulfuric acid, etc. A thing etc. are used preferably.

  Further, in the molding process, a resin having a softening point lower than the higher softening point of the synthetic resin film for molding or the transparent or translucent thermoplastic resin film layer so that the decorative layer is sufficiently stretched Is preferred. More preferably, the difference is 20 ° C. or more. By using these binder resins, the decorative layer in the laminated sheet can be prevented from being easily agglomerated and peeled off.

  In addition to these binder resins, acrylic resins, vinyl chloride resins, vinylidene chloride resins, vinyl chloride-vinyl acetate resins, ethylene-vinyl acetate, which are generally used in inks or paints, as long as they do not impair the spirit of the present invention. A resin, polyolefin resin, chlorinated olefin resin, ethylene-acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, or polyester resin may be used in combination.

(solvent)
The solvent used for the high gloss ink used for the decorative layer will be described. The binder resin described above, in particular, a binder resin containing any one or more groups of carboxyl group, phosphoric acid group, sulfonic acid group, sulfonic acid group and their metal salts and amino groups has a relatively high polarity, In order to dissolve them, the solubility parameter cannot be dissolved unless the solvent is in the range of 8.6 to 10.3. However, in the case of a transparent or translucent thermoplastic resin film, an acrylic film, or a polycarbonate film, the solvent in this range also swells and deteriorates these films and impairs the gloss of the coated decorative layer. In addition to this, the gloss during molding tends to decrease. However, the solvent for the high gloss ink contains 50% by mass or more of the organic solvent having a solubility parameter of 8.6 or less and at least one alcohol selected from lower monoalcohols having 1 to 5 carbon atoms. It is found that if a mixed solvent is used and the solubility parameter of the mixed solvent is 8.6 to 10.3, a binder resin having a high polarity is dissolved and a base material such as an acrylic resin or a polycarbonate resin is not affected. It was. In other words, the solvent for the high-gloss ink used in the laminated sheet for molding of the present invention is selected from the following viewpoints among known conventional solvents used in conventional gravure inks, flexo inks, screen inks, paints, and the like. be able to. Specifically, those having a solubility parameter of 8.6 or less include, for example, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, butyl acetate, isobutyl acetate, amyl acetate, methyl isobutyl ketone, ethylene glycol monoethyl ether And alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether. The lower monoalcohols having 1 to 5 carbon atoms include methanol (solubility parameter: 14.5), ethanol (12.7), isopropyl alcohol (11.5), and normal propyl alcohol (11.9). ), Normal butyl alcohol (11.4), isobutyl alcohol (11.1), 2-butyl alcohol (10.8), t-butyl alcohol (10.6), amyl alcohol ( Id: 10.9). And isoamyl alcohol (same as 10.0). It should be noted that aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and propyl acetate, ketones such as acetone and methyl ethyl ketone, and the like can be used in combination without departing from the spirit of the present invention.

(Additive)
High gloss ink used in the decorative layer, if necessary, defoaming, settling prevention, pigment dispersion, fluidity modification, blocking prevention, antistatic, Various additives used in conventional gravure inks, flexo inks, screen inks, paints and the like can be used for the purpose of preventing oxidation, light stability, ultraviolet absorption, internal crosslinking, and the like. Examples of such additives include coloring pigments, dyes, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, chelating agents, polyisocyanates, and the like.

(Colorant)
A colorant can be used in the high gloss ink layer as long as the design of the mirror-like metallic luster is not impaired. As the colorant, a pigment is preferably used. The pigment to be used is not particularly limited, and pigments known per se such as a color pigment, a metallic pigment, an interference color pigment, a fluorescent pigment, and an extender pigment can be used. Examples of the color pigment include organic pigments such as quinacridone series such as quinacridone red, azo series such as pigment red, phthalocyanine series such as phthalocyanine blue and phthalocyanine green, and perylene series such as perylene red; inorganic such as titanium oxide and carbon black Pigments. Examples of metallic pigments include aluminum powder, nickel powder, copper powder, brass powder, and chromium powder.

  Examples of the interference color pigment include pearly luster-like pearl mica powder and pearly luster-like colored pearl mica powder. Examples of the fluorescent pigment include a synthetic resin solid solution type in which a fluorescent dye such as basic yellow or rhodamine B is dissolved in a melamine resin or the like. Examples of extender pigments include inorganic pigments such as barium sulfate and calcium carbonate. The pigment can be added directly, or it can be added as a colorant for plastics such as a color compound, concentrated masterbatch, powder colorant, granular colorant, liquid colorant and the like.

(Design layer)
The molded laminated sheet of the present invention has a decorative layer and a transparent or translucent thermoplastic resin film layer, or a decorative layer, as long as it does not impair the specular metallic luster of the high gloss ink layer. Between the synthetic resin film layers for molding, a colored layer can be provided on the entire surface or a part thereof. Alternatively, regular or irregular irregularities may be provided on the surface of the transparent or translucent thermoplastic resin film layer to express a hologram or matte design. The above-mentioned colorant can be used for the colored layer, and as the binder resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinyl acetate resin, ethylene-vinyl acetate generally used for ink or paint are used. Resins, polyolefin resins, chlorinated olefin resins, ethylene-acrylic resins, polyurethane resins, polyamide resins, urea resins, epoxy resins, and polyester resins can be used.

(Preparation method of high brightness ink)
Generally, in order to stably disperse the ink blending raw material, the pigment and other additives are finely divided to submicron by kneading using a roll mill, ball mill, bead mill, or sand mill. However, the metal thin film strips to be incorporated in the high gloss ink used for the decorative layer of the laminate sheet for molding of the present invention in order to develop a metallic luster preferably have a particle size of 5 to 25 μm. When the above-mentioned kneaded meat is performed, the metal thin film pieces become fine particles, and the metallic luster is extremely lowered. Therefore, in the present invention, it is desirable not to perform kneading but to simply mix the above-mentioned blended raw materials with a mixer or the like to obtain a high gloss ink.

(Printing or coating method)
The decorative layer of the laminate sheet for molding of the present invention, the ink layer that may be further laminated to the decorative layer, and the printing or coating method of the adhesive are printing methods such as gravure printing, flexographic printing, screen printing, gravure coater, Coating methods such as a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, an air knife coater, a kiss touch coater, a kiss touch reverse coater and a comma coater, a comma reverse coater, and a micro gravure coater can be used. Of these, a gravure reverse coater, a kiss touch reverse coater, a comma coater, and a micro gravure coater are preferable.

(Synthetic resin film layer for molding)
The molding laminated sheet of the present invention can be vacuum-molded as it is and inserted into a mold for injection molding. However, depending on the type of resin to be injected, there may be a problem in adhesion. It is preferable to provide a synthetic resin film layer for molding having adhesiveness with the resin to be formed on the back side. The synthetic resin film layer for molding is preferably a film mainly composed of a thermoplastic resin when performing a molding process by heat such as vacuum molding.

  As the synthetic resin film layer for molding, for example, acrylonitrile / butadiene / styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, polyethylene (PE) resin, General-purpose resin such as polypropylene (PP) resin, vinyl chloride (PVC) resin, olefin elastomer (TPO), vinyl chloride elastomer (TPVC), styrene elastomer (SBC), urethane elastomer (TPU), polyester Thermoplastic elastomers (TPE) such as polyamide elastomer (TPEE) and polyamide elastomer (TPAE) can be used. These materials may be used alone, or may be used by mixing (blending) two or more materials, or may be used as a laminated sheet obtained by co-extruding materials having different characteristics.

(Laminated)
A synthetic resin film layer for molding selected from the various resin films or sheets described above is further laminated on the printed or coated decorative layer. This lamination method may be a method using an adhesive at the interface between the decorative layer and the synthetic resin film layer for molding, or a method not using it. As the adhesive, a dry laminate adhesive, a wet laminate adhesive, a heat seal adhesive, a hot melt adhesive, or the like is preferably used. Moreover, the heat laminate which does not use a special adhesive bond layer may be sufficient. In this case, a resin having adhesiveness at normal temperature to about 60 ° C. may be used as the binder resin for the decoration layer.

(Adhesive)
Moreover, it can replace with an adhesive bond layer and can also provide an adhesive layer. As the adhesive, acrylic, rubber, polyalkyl silicon, urethane, polyester, and the like are preferably used.

(Surface protective layer)
In the laminated sheet for molding of the present invention, performance such as designability, friction resistance, scratch resistance, weather resistance, stain resistance, water resistance, chemical resistance and heat resistance is imparted to the surface layer side during molding. In order to do so, one or more transparent, translucent or colored clear topcoat layers may be provided. As the topcoat agent, a lacquer type, a crosslinking type by isocyanate or epoxy, a UV crosslinking type or an EB crosslinking type is preferably used as long as the stretchability of the laminated sheet for molding is not inhibited.

(Use)
The molding laminated sheet of the present invention can be used as a surface layer in various molding methods. For example, after placing a transparent or translucent thermoplastic film on the surface side to form a preform having a three-dimensional shape by thermoforming, it is inserted into an injection mold and integrated with the injection resin. It can be molded by insert injection molding. Furthermore, it can also be molded by an in-mold injection molding method in which a sheet is inserted into an injection mold and integrated with an injection resin in the mold. Due to the excellent stretchability of the molding laminate sheet of the present invention, it is possible to maintain a design property having an excellent mirror-like metallic luster even at a portion where the degree of stretching is large.

  In the present invention, stretchability is defined as follows. After the molding process is performed at a temperature higher than the softening point of the material constituting the molding laminate sheet, the thickness of the molding laminate sheet is measured, and the thickness is ½ of the thickness before the molding process. The part having the area, that is, the part whose area is doubled is referred to as a 200% stretched part. Similarly, after stretching, the portion where the thickness is 1 / 1.3 times, that is, the area becomes 1.3 times is a 130% stretched portion, and the thickness is 1 / 1.5 times, that is, the area is 1.5 times. The gloss was measured with the portion to be 150% stretched.

(High brightness)
In the present invention, the change in high brightness of the stretched sheet is measured by using a gloss meter: mirror-TRI-gloss (manufactured by BYK Gardner) from the transparent or translucent thermoplastic film side at 20 ° / It is defined as the rate of change of the surface gloss value measured at 20 °.
Change rate of surface gloss value = (Gloss value of non-stretched portion−Gloss value of stretched portion) ÷ (Gloss value of non-stretched portion) × 100 (%)

  When the stretch ratio was 130%, the forming process was performed using a test mold having a bottom surface of 126 mm on one side and a front edge of 160 mm on one side and a depth of 35 mm so that the bottom surface portion was stretched 130%. Similarly, when the stretch rate was 150%, a test mold having a bottom surface of 126 mm on one side and a front edge of 160 mm on one side and a depth of 40 mm was used to process the bottom portion to 150%. Furthermore, when the stretching ratio was 200%, a test mold with a bottom surface of 126 mm on one side and a front edge of 160 mm on one side and a depth of 55 mm was used so that the bottom surface portion was stretched by 200%.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The part and% in an Example represent a mass part and the mass%.
(1) Aluminum thin film strip nitrocellulose (HIG7) was dissolved in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to obtain a 6% solution. The solution was applied onto a polyester film with a gravure plate having a screen line number of 175 lines / inch and a cell depth of 25 μm to form a release layer. After sufficiently drying, aluminum is vapor-deposited on the release layer to a thickness of 0.03 μm, and the same nitrocellulose solution as that used for the release layer is applied to the deposited film surface under the same conditions as in the release layer. The top coat layer was formed by coating.

  The deposited film is immersed in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to peel the aluminum deposited film from the polyester film, and then the aluminum deposited film is pulverized with a stirrer so that the size becomes about 150 μm. An aluminum thin film strip was prepared.

(2) Aluminum thin film strip slurry Aluminum thin film strip 10 parts Ethyl acetate 35 parts Methyl ethyl ketone 30 parts Isopropyl alcohol 30 parts While mixing and stirring the above, 5 parts of a nitrocellulose solution having the following composition was added.

Nitrocellulose (HIG 1/4) 25%
Ethyl acetate: isopropyl alcohol = 6: 4 mixed solvent 75%
While maintaining the temperature at 35 ° C. or lower, the above mixture is stirred using a turbo mixer until the size of the aluminum thin film pieces becomes 5 to 25 μm, thereby preparing an aluminum thin film piece slurry (nonvolatile content 10%). did.

(4) High glitter ink (High glitter ink preparation example B-1)
Aluminum thin film slurry (non-volatile content 10%) 30 parts Binder Resin Carboxylic acid-containing PVC-vinyl acetate resin (Dow Chemical Co., Ltd.)
"UCAR VMCH") 3 parts
Carboxylic acid-containing urethane resin (Dainippon Ink & Chemicals, Inc.
"Tyforth NT-810-45" non-volatile content 45%) 6 parts methyl isobutyl ketone 12 parts butyl acetate 23 parts isopropanol 10 parts The above was mixed to prepare high gloss ink B-1.
The total of the solubility parameter 8.6 or less solvent (methyl isobutyl ketone, butyl acetate) and C1-C5 monoalcohol (isopropanol) was 71.3%, and the average solubility parameter of the mixed solvent was 9.5. .

(High brightness ink preparation example B-2)
Aluminum thin film slurry (non-volatile content 10%) 30 parts Binder resin Carboxylic acid-containing vinyl chloride-vinyl acetate resin manufactured by Dow Chemical Company
"UCAR VMCH") 3 parts
Carboxylic acid-containing urethane resin (Dainippon Ink & Chemicals, Inc.
"Tyforth NT-810-45" non-volatile content 45%) 6 parts Ethyl acetate 30 parts Isopropanol 15 parts The above was mixed to prepare high gloss ink B-2.
The sum of the solvent having a solubility parameter of 8.6 or less and a monoalcohol having 1 to 5 carbon atoms (isopropanol) was 31.4%, and the average solubility parameter of the mixed solvent was 9.9.

(5) Adhesive (adhesive preparation example)
2 parts comprising 100 parts of aromatic polyether urethane resin (Dick Dry AS-106A: manufactured by Dainippon Ink and Chemicals) as the main agent and 10 parts of epoxy (LR-100: manufactured by Dainippon Ink and Chemicals) as the curing agent. A liquid adhesive D-1 was obtained.

  As transparent thermoplastic resin film, transparent, surface gloss value of 150 (60 ° / 60 °), rubber-modified PMMA film (hereinafter referred to as film A) with a thickness of 125 μm, and as synthetic resin film for molding, gray and opaque An ABS film (hereinafter referred to as film C) having a thickness of 300 μm was used.

Example 1
The layer structure is film A / high gloss ink B-1 / adhesive D-1 / film C, and the high gloss ink B-1 is coated and dried with a kiss reverse coater so that the dry film thickness is 2.0 μm. Thereafter, the adhesive D-1 was applied to a coating amount of 5.0 g / m ² with a gravure coater, and the film C was immediately laminated. The obtained laminated sheet for molding was aged at 40 ° C. for 3 days, and thereafter molded by a vacuum molding method under the conditions of a sheet temperature of 155 ° C. and a mold temperature of 60 to 80 ° C.

(Comparative Example 1)
The layer constitution is film A / high gloss ink B-2 / adhesive D-1 / film C, and the high gloss ink B-2 is coated with a kiss reverse coater so that the dry film thickness is 2.0 μm. After drying, the adhesive D-1 was applied to a coating amount of 5.0 g / m ² with a gravure coater, and the film C was immediately laminated. The obtained laminated sheet for molding was aged at 40 ° C. for 3 days, and thereafter molded by a vacuum molding method under the conditions of a sheet temperature of 155 ° C. and a mold temperature of 60 to 80 ° C.

The laminated sheet for molding having a specular metallic luster design of the present invention can be usefully applied particularly as a surface base material for automobile-related members, building material members, home appliances and the like.

Claims (6)

A method for producing a laminated sheet for molding comprising a transparent or translucent thermoplastic resin film layer and a decorative layer having a mirror-like metallic luster, wherein the decorative layer forming step comprises metal thin film strips, binding Resin, an organic solvent having a solubility parameter of 8.6 (cal / ml) ^(1/2) or less, and one or more alcohols selected from lower monoalcohols having 1 to 5 carbon atoms are combined. It has a coating process and a drying process of high-brightness ink containing a mixed solvent containing at least mass% and having a solubility parameter of 8.6 to 10.3 (cal / ml) ^(1/2) A method for producing a laminated sheet. 2. The production of a laminated sheet for molding according to claim 1, wherein the binder resin in the high gloss ink has one or more of a carboxyl group, a phosphoric acid group, a sulfonic acid group, a metal salt thereof, and an amino group. Way . The method for producing a laminated sheet for molding according to claim 1, wherein the transparent or translucent thermoplastic resin film layer is a thermoplastic resin film layer mainly composed of an acrylic resin. The manufacturing method of the shaping | molding laminated sheet of Claim 1 which has a synthetic resin film layer for shaping | molding further on the above-mentioned decoration layer side. The molding synthetic resin film described above has thermoplasticity, and the softening point of the binder resin of the decoration layer described above is the higher of the molding synthetic resin film or the transparent or translucent thermoplastic resin film layer described above. The method for producing a laminated sheet for molding according to any one of claims 1 to 4, wherein the method has a lower softening point. The rate of change of the surface gloss value on the transparent or translucent molding thermoplastic resin film layer side when the laminate sheet for molding is 200% stretch-molded is 30% or less. The manufacturing method of the lamination sheet for a description of description.