JP2006281451A - Molding laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding laminated sheet having good design properties having a depth feeling by a simple layered constitution and also having stretchability required at the time of molding. <P>SOLUTION: In a colored molding laminated sheet having a transparent or translucent color layer and a metal gloss layer having metal gloss laminated in this order from its surface layer side, (a) the luminosity L<SP>*</SP>of the transmitted light of the color layer is 20-80, (b) the gloss value of the metal gloss layer is 200 or above and (c) the chroma C<SP>*</SP>of the regular reflected light of 45° on the surface layer side of the molding laminated sheet is 150 or above. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate sheet for molding having a design feeling with a sense of depth, and particularly to a laminate sheet for molding 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. Recently, high-quality designs such as a design with a sense of depth have been demanded for molded members. “Deep feeling” means to feel light reflection from a layer deeper than the actual coating thickness when visually observed. The design with the least depth is when the member is opaque and the light is reflected directly on the surface. Generally, in order to obtain a design with a depth, a relatively thick clear layer is placed on the outermost surface. A colored layer is provided therebelow. However, since it only feels the depth of the actual coating thickness, when a design with a deeper feeling is required, for example, in the case of a coating method, a transparent or translucent colored layer containing a bright coloring material and Several layers of transparent resin layers are alternately applied, transmission from the coating layer, phase difference is provided in the reflected light, and the like (for example, see Patent Document 1). However, this method requires time and effort to apply different types of paints, and the reflected light from the lower layer is too weak to provide a sufficient depth feeling. In order to obtain a deep feeling, it is necessary to use a dark colored layer, but the reflected light from the lower layer is weakened. This is because a normal pigment has a particle diameter larger than that of visible light, and incident light is scattered. This scattering can be prevented by using a dye, but the dye has insufficient weather resistance and is not practical.

  Furthermore, the “feeling of depth” is based on a human personal sense, and it has been difficult to quantify this conventionally.

JP-A-6-126239

  An object of the present invention is a laminated sheet for molding that does not require a coating process including solvent spraying, etc., and has a design with a good sense of depth due to a simple layer structure, and also has the stretchability required at the time of molding. It is providing the molded object which shape | molded using the laminated sheet for shaping | molding which has, and the obtained laminated sheet for shaping | molding.

In order to solve the above problems, the present inventors have studied various laminated sheets for molding, and as a result, a laminated sheet for molding having a specific colored layer and a metallic gloss layer is obtained.
a) The lightness L ^* of the transmitted light of the transparent or translucent colored layer is 80 or less,
b) The gloss value of the metallic luster layer is 200 or more,
c) When the saturation C ^* of 45 ° specular reflection light on the surface side of the laminated sheet for molding satisfies 150 or more, it is found that the majority of people feel “depth” and solves the present invention. It came to.
That is, in the present invention, a transparent or translucent colored layer and a metallic gloss layer having a metallic luster are laminated in this order from the surface layer side in the laminated sheet for colored molding,
a) The lightness L ^* of the transmitted light of the colored layer is 20 to 80,
b) The gloss value of the metallic luster layer is 200 or more,
c) A laminated sheet for molding in which the chroma C ^* of 45 ° specular reflection light on the surface layer side of the molded sheet is 150 or more.

  The laminated sheet for molding of the present invention can provide a molded product having a design with a sense of depth by thermoforming.

The colored layer included in the laminated sheet for molding provided by the present invention is not limited to a colored layer (hereinafter referred to as a color layer), but may be a laminated structure having the following mode.
1) Transparent or translucent color layer (single layer)
As shown in FIG. 1, it has the transparent or translucent color layer 1, and the metallic luster layer 2 which has metallic luster.
2) Laminated structure of transparent or translucent thermoplastic resin layer and transparent or translucent color layer As shown in FIG. 2, the thermoplastic resin layer 4 and the color layer 1 are colored layers.
3) Laminated structure of transparent or translucent thermoplastic resin layer, transparent or translucent color layer, and transparent or translucent cured product layer, as shown in FIG. 3, thermoplastic resin layer 4, color layer 1 and cured The physical layer 5 is a colored layer.
However, in order to have a sense of depth which is the effect of the present invention, the colored layer needs to have a specific transmittance and a lightness L ^* of 20 to 80.

(Colored layer)
The colored layer of the present invention has a lightness L ^{* of} transmitted light transmitted through the layer of 20 to 80, and provides a design with a sense of depth when combined with a metallic gloss layer having a high gloss value described later.

The colored layer of the present invention includes a color layer that is a colored layer as an essential component. Examples of the color layer include a layer containing a transparent binder resin and a transparent or translucent colorant as constituent components, and a layer made of printing ink having a normal colorant. The term “transparent” or “translucent” as used herein means that the lightness L ^{* of} transmitted light transmitted through the colored layer is 20 or more, preferably 30 or more.

(Coloring material)
As the transparent or translucent colorant used in the present invention, a pigment or a dye can be used. Of these, pigments are preferred from the viewpoint of weather resistance.

As the pigment, known pigments can be used, but in order to obtain a transparent colored layer, it is preferable that the average particle diameter of the pigment is small. The transparency of the pigment increases as the particle size decreases. The average particle size of the pigment used in the present invention is preferably 300 nm or less, more preferably in the range of 5 to 200 nm, as determined by the dynamic light scattering method. If the particle size is less than 5 nm, the cohesiveness of the pigment becomes high and difficult to disperse, and the coating liquid is unstable. If it exceeds 300 nm, the transparency is lowered, and the incident light is scattered and the metal gloss layer is sufficient. It becomes difficult to reach. Incident light that has reached the metallic luster layer is reflected by the mirror-like metallic luster layer and enters the eyes of the observer as light having a phase different from that of the incident light reflected in the colored layer, thereby obtaining a “depth”. it is conceivable that.

As a pigment to be used, a known pigment such as a color pigment, a metallic pigment, an interference color pigment, or a fluorescent 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.
These pigments can generally be made into fine particles by physical pulverization, but conversely, they can also be obtained by crystallization on the surface of several μm silicon particles or the like.

  Examples of the interference color pigment include pearly luster pearl mica powder, pearly luster colored pearl mica powder, and the like. 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. The pigment can be added directly or as a plastic colorant such as a color compound, concentrated masterbatch, powder colorant, granular colorant, liquid colorant or the like. In addition, a pigment may use only 1 type and may use 2 or more types. However, since these interference color pigments may deteriorate the transparency, it is necessary to add them in such an amount that the transparency or translucency can be maintained.

  As the binder resin used in the colored layer, those conventionally used in conventional gravure ink, flexo ink, screen ink, paint, and the like can be used. It may be a thermosetting resin or a thermoplastic resin. 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 polyurethane resin for paint Polyamide resin, urea resin, epoxy resin, polyester resin, petroleum resin, cellulose derivative resin and the like are preferably used. These binder resins may be used alone or in combination with a curing agent such as isocyanate, melamine, or epoxy. In order to improve the dispersion of the transparent pigment, those resins in which polar groups such as carboxyl group, phosphoric acid group, sulfonic acid group, amino group and quaternary ammonium base are chemically bonded are used or used in combination. May be.

The transparent or translucent colored layer may be composed of a cured product in a semi-cured state of a curable resin containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound.

Also, if necessary, defoaming, settling prevention, pigment dispersion, fluidity modification, blocking prevention, antistatic, antioxidation, light stability, UV absorption, internal absorption, as long as design properties and stretchability are not hindered For the purpose of crosslinking and the like, various additives used in conventional inks or paints can be used. Examples of such additives include coloring pigments, dyes, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, chelating agents, polyisocyanates, and the like.

(Glossy metallic layer)
The light that has passed through the colored layer is reflected by the metallic luster layer and enters the viewer's eyes as light with a phase different from the incident light reflected in the colored layer. The gloss value of the metallic gloss layer is preferably 400 or more, and more preferably 800 or more.

The decorative layer of the laminated sheet for molding according to the present invention can be formed by vapor deposition or printing or coating with high-brightness ink in which metal thin film strips are dispersed in a binder resin.

(Vapor deposition)
The glossy metallic layer formed by vapor deposition can have a high gloss value in the state of the laminated sheet before molding, but since the stretchability of the vapor deposition surface is not sufficient, it is subjected to molding such as vacuum molding or in-mold molding. In this case, cracks and uneven gloss may occur, and the glossiness may be significantly reduced. It is preferable to use it by vapor deposition using a material that does not easily crack (for example, indium) or molding at a low deep drawing rate. For molding at a high deep drawing ratio, a laminated sheet for molding in which a gloss layer is formed with a high gloss ink described later is preferable.

(High gloss ink)
It is formed by printing or coating a high-brightness ink in which metal thin film strips are dispersed in a binder resin varnish on a color layer or a cured product layer described later. Examples of the high gloss ink include gravure ink, screen ink, and the like, and gravure ink is preferable in order to orient the metal thin film strips uniformly and in parallel. Content with respect to the non volatile matter in the ink of a metal thin film strip is 10-60 mass%, Preferably it is the range of 20-45 mass%. Normally, metallic powder is used for metallic inks, but when thin metal strips are used, the result of the metal thin strips being oriented parallel to the surface of the object when the ink is printed or applied. Thus, a high-luminance decorative layer that cannot be obtained with conventional metal powders can be obtained.

  The metal of the metal thin film strip used for the high gloss ink used in the metallic gloss layer is not particularly limited. For example, aluminum, gold, silver, copper, titanium, chromium, nickel, indium, molybdenum, tungsten, palladium, iridium , Silicon, tantalum, nickel chromium, chromium copper, aluminum silicon, brass, stainless steel, and the like. Only 1 type may be used and 2 or more types may be mixed and used. 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, and more preferably 0.02 to 0.045 μm. The particle diameter of the metal thin film pieces dispersed in the ink is preferably 5 to 25 μm, more preferably 10 to 15 μm. When the particle size is less than 5 μm, the gloss of the coating film is insufficient, and when it exceeds 25 μm, the metal thin film strips are difficult to be oriented, so that the gloss is lowered and the ink is printed or applied by a gravure method or a screen printing method. Doing so may cause clogging of the plate. The particle size of the metal thin film strip can be measured by a Coulter counter method, a microscope observation method, a laser diffraction method, or the like, and the average size of the planar portion of the thin film strip is defined as the particle size.

  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 coating layer is applied to the surface of the deposited film to prevent oxidation. The same coating agent for forming the release layer and the coat layer can be used.

  Resin used for a peeling layer or a coating 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. Examples of the solvent for the resin 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. Alcohols such as alcohol, ketones such as acetone and methyl ethyl ketone, alkylene glycol monoalkyl ether such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, and the like can be used.

  The metal vapor deposition film is immersed in a solvent that dissolves the release layer and the coat layer and stirred. After the metal vapor deposition film is peeled from the support film, the metal thin film is further stirred to reduce the particle size of the metal thin film pieces to about 5 ˜25 μm, preferably 10 to 15 μm, filtered and dried. The solvent is not particularly limited except that it dissolves the resin used for the release layer or the coat layer. Even when the metal thin film is formed by sputtering, the metal thin film strip can be obtained 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 surface-treated in order to enhance dispersibility in the ink. 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.

  As the binder resin used for the high gloss ink, those conventionally used in conventional gravure ink, flexo ink, screen ink, paint, and the like 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 polyurethane resin for paint Polyamide resin, urea resin, epoxy resin, polyester resin, petroleum resin, cellulose derivative resin and the like are preferably used. In addition, those obtained by chemically bonding polar groups such as carboxyl group, phosphoric acid group, sulfonic acid group, amino group and quaternary ammonium base to these resins may be used or used in combination.

  For high-brightness inks, defoaming, settling prevention, pigment dispersion, fluidity modification, anti-blocking, antistatic, antioxidation, light stability in the ink are required as long as the design and stretchability are not impaired. Various additives used in conventional gravure inks, flexographic inks, screen inks, paints and the like can be used for the purpose of 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. The film thickness of the high glitter ink layer can be arbitrarily determined, but is preferably 0.05 to 3 μm, more preferably 0.5 to 2 μm, and further preferably 1 to 2 μm.

  The high gloss ink is a solvent-based ink, and the solvent used in the ink can be a known conventional solvent used in conventional gravure ink, flexo ink, screen ink, paint or the like. Specifically, for example, 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, isopropyl alcohol and the like 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.

  When the binder resin and the metal thin film strip are mixed and then subjected to kneading such as a roll mill, the metal thin film strip becomes fine particles, and the metallic luster is extremely lowered. Therefore, in the present invention, kneading is not performed, and the above-mentioned blended raw materials consisting of the binder resin, the metal thin film strip and the solvent are simply mixed with a mixer to obtain an ink.

(Cured product layer)
As shown in FIG. 3, the laminated sheet for molding of the present invention is a cured product composed of a cured product of a semi-cured state of a curable resin between a transparent or translucent color layer 1 and a metallic luster layer 2. The physical layer 3 may be included. The cured product layer is preferably a semi-cured cured product of a curable resin containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound. In particular, when the metallic luster layer is formed by printing or coating a high-brightness ink in which metal thin film strips are dispersed in a binder resin varnish, the solvent contained in the high-brightness ink attacks the colored layer. This is preferable because it can prevent the loss of transparency and the like.

When a transparent or translucent thermoplastic acrylic resin film is used as the surface layer from the standpoint of ease of integral molding, surface hardness, and weather resistance, when high gloss ink that forms a metallic luster layer is printed or applied directly Particularly, it is easily eroded by the organic solvent contained in the high gloss ink. When the interface between the colored layer and the metallic luster layer loses smoothness due to erosion, the orientation of the metal thin film strips forming the metallic luster layer is not parallel to the printed or coated surface, and the design with a sense of depth is impaired. Cheap. The cured product layer can protect the colorant layer interface from the solvent contained in the high-gloss ink used to form the metallic gloss layer, and can keep the interface with the metallic gloss layer smooth. The cured product layer fills minute irregularities of the colored layer, increases adhesion with the colored layer, and improves the smoothness of the interface with the metallic luster layer. Even if the solvent contained in the composition forming the cured product layer erodes the interface of the colored layer, there is no problem because the cured product layer itself forms a smooth surface.

  The curable resin forming a semi-cured state used for the cured product layer of the laminated sheet for molding of the present invention has a hydroxyl group-containing acrylic from the viewpoint of easy adjustment of the crosslinking reaction, weather resistance, adhesion to the colored layer, and the like. A curable resin containing a resin and a polyisocyanate compound is preferred.

The cured product layer can improve the solvent resistance against the solvent contained in the high gloss ink used to form the metallic luster layer, and the cured product layer has heat resistance, and the heat resistance makes thermoforming Sometimes, it is a resin layer that forms a substantially transparent film having crack resistance that does not cause cracking in the laminated sheet for molding as well as the cured product layer itself. In the present invention, the semi-cured state means that the above-mentioned semi-cured cured product contains unreacted hydroxyl group and isocyanate group, and the hydroxyl group and isocyanate in the hydroxyl group-containing acrylic resin described above. The reaction rate of the isocyanate group in the reaction with the isocyanate group in the compound means 50 to 80%, preferably 60 to 80%, more preferably 60 to 75%. The reaction rate can be measured with an infrared spectrophotometer.

  More specifically, the hydroxyl group-containing acrylic resin has a hydroxyl value of 10 to 100, more preferably 40 to 100, a weight average molecular weight (polystyrene equivalent value) of 10,000 to 200,000, and a glass transition temperature (Tg). Is preferably a hydroxyl group-containing acrylic resin having a temperature of 70 to 120 ° C, more preferably 75 to 115 ° C.

  By setting the hydroxyl value to 10 or more, the crosslinking polymer has a sufficient crosslinking density and tends to have good hardness and acid resistance. By setting the hydroxyl value to 100 or less, the three-dimensional formability is improved. There is a tendency. A particularly preferred range of this hydroxyl value is in the range of 30-100.

  When the weight average molecular weight is 10,000 or more, the solvent resistance of the cured product layer tends to be good. When the weight average molecular weight exceeds 200,000, the leveling property is lowered and the gloss of the metallic luster layer is increased. Decreases. This weight average molecular weight is more preferably in the range of 20,000 to 100,000. Moreover, it is preferable that the glass transition temperature (henceforth Tg) induced | guided | derived by the formula of fox of a hydroxyl-containing acrylic resin is 70-120 degreeC. By setting Tg to 70 ° C. or higher, the three-dimensional formability tends to be good.

  In order to prepare the above hydroxyl group-containing acrylic resin, a known and usual method can be used. Among them, if only typical ones are exemplified, the acrylic monomer having a hydroxyl group is mainly selected, and further selected as needed, other copolymerizable with the acrylic monomer. A method of copolymerizing with a monomer can be used.

  As specific examples of the acrylic monomer having a hydroxyl group, which is used as necessary when preparing the acrylic resin used in the present invention according to the above-described method, for example, 2-hydroxyethyl acrylate, Acrylic acid or 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc. C2-C8 hydroxyalkyl ester of methacrylic acid; monoester of polyether polyol such as polyethylene glycol, polypropylene glycol, polybutylene glycol and the like and unsaturated carboxylic acid such as acrylic acid or methacrylic acid; hydroxyethyl Hydroxyalkyl vinyl ethers such as nyl ether; allyl alcohol; adducts of α, β-unsaturated carboxylic acids and monoepoxy compounds such as α-olefin epoxides; polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol And monoethers of hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate; glycidyl acrylate or glycidyl methacrylate and acetic acid, propionic acid, p-tert-butylbenzoic acid, fatty acids and the like And adducts with monobasic acids; adducts of the above hydroxyl group-containing monomers with lactones (for example, ε-caprolactone, γ-valerolactone, etc.).

  Other monomers copolymerizable with these include n-propyl methacrylate, isopropyl methacrylate, methacrylic acid (n-, iso- or tert-) butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, C1-C22 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate , Methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc., acrylic acid or methacrylic acid alkoxyalkyl ester having 2 to 18 carbon atoms; N, N-dimethyl Aminoalkyl acrylic esters such as ruaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate; acrylamide, methacryl Acrylamide monomers such as amide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; acrylic acid, methacrylic acid, etc. Unsaturated monocarboxylic acid; carboxyl group-containing monomers such as maleic acid, itaconic acid, fumaric acid, mesaconic acid and unsaturated dicarboxylic acids such as acid anhydrides and half-esterified products thereof or modified products thereof; Anhydrous itacone Monoester or diesterified products of acid anhydride group-containing unsaturated compounds such as ethylene glycol, 1,6-hexanediol, neopentyl glycol and the like; glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate Vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; ethylene, propylene, 1-butylene, 2-butylene, acrylonitrile, vinyl acetate, vinyl chloride and the like.

  In order to prepare a hydroxyl group-containing acrylic resin using the monomers as mentioned above, various known and conventional polymerization methods such as solution polymerization method, non-aqueous dispersion polymerization method and bulk polymerization method are used. Can be applied. Among them, the radical polymerization method in an organic solvent, that is, the solution radical polymerization method is recommended because it is the simplest.

  Examples of the production method include aromatic hydrocarbons such as xylene and toluene, alcohols such as isopropyl alcohol, isobutanol and n-butanol, esters such as ethyl acetate and butyl acetate, and ketones such as methyl amyl ketone. Radical polymerization initiators such as azo compounds such as N, N-azobisdiisobutyronitrile and organic peroxides such as benzoyl peroxide in organic solvents such as ethers such as cellosolve, butyl cellosolve and cellosolve acetate, n- The above-mentioned monomer component is reacted at a reaction temperature of about 60 to 160 ° C. for about 1 to 30 hours using a chain transfer agent such as dodecyl mercaptan.

  The polyisocyanate compound used for forming a cured product layer composed of a curable resin in a semi-cured state, which is used in the laminated sheet for molding of the present invention, has an average of two or more isocyanate groups in one molecule, and The number average molecular weight (polystyrene equivalent value) is preferably 10,000 or less. More preferably, it is 150 or more and 5,000 or less, and particularly preferably 2,000 or less. In the present invention, “having two or more isocyanate groups on average in one molecule” means that the polyisocyanate compound to be used contains three or more isocyanate groups in one molecule, so-called trivalent or higher isocyanate. It means that the compound is contained as an essential isocyanate compound component.

  Specific examples of these trivalent or higher isocyanate compounds include 2-isocyanatoethyl-2,6-diisocyanatocaproate, 1,3,5-triisocyanatocyclohexane, 2,4,6-triisocyanate. Aliphatic triisocyanates such as cycloheptane and 1,2,5-triisocyanatocyclooctane; Aromatic triisocyanates such as 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatonaphthalene; And polyisocyanates having a so-called isocyanurate ring structure obtained by cyclization and trimerization. As compound B, it is preferable to use divalent isocyanate compounds, that is, diisocyanates, in combination with these trivalent or higher organic polyisocyanate compounds.

  These diisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2 -Cyclic aliphatic diisocyanates such as methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, methylenebis (cyclohexyl isocyanate), isophorone diisocyanate; tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate , M-xylylene diisocyanate, 4,4'-diphenylmethane di Socia sulfonates xylylene diisocyanate, α, α, α ', α'- tetramethyl -m- xylylene diisocyanate, tetramethylxylylene diisocyanate, aromatic diisocyanates such as naphthalene diisocyanate.

  Further, trivalent or higher polyisocyanate compounds can be used in combination with the following. For example, a polyisocyanate compound having a valence of 3 or more is a dimer or a trimer of a polyisocyanate having a valence of 2 or more; a diisocyanate having a valence of 3 or more and a polyhydric alcohol, a low molecular weight polyester resin, water, or the like. Adducts obtained by reacting with an excess of isocyanate groups, etc .; free isocyanate groups of isocyanate compounds having free isocyanate groups were blocked with blocking agents such as phenols, oximes, lactams, alcohols, mercaptans, etc. Block polyisocyanate; polyisocyanate having biuret structure obtained by reacting polyisocyanate having free isocyanate group with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α -Dimethylbenzyl isocyanate Homopolymers of vinyl monomers having an isocyanate group, such as anate or (meth) acryloyl isocyanate, or (meth) acrylic and vinylester-based copolymers of these isocyanate group-containing vinyl monomers. Isocyanate group-containing acrylic copolymer, vinyl ester copolymer or fluoroolefin copolymer obtained by copolymerization with vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers, respectively. It can be used in combination with various vinyl copolymers such as polymers.

  The compounding ratio of the hydroxyl group-containing acrylic resin and the polyisocyanate compound used for forming the cured product layer used in the laminated sheet for molding of the present invention is a polyisocyanate compound per one hydroxyl group equivalent in the hydroxyl group-containing acrylic resin. A range of 0.3 to 2.0 equivalents of the isocyanate group is preferable from the balance of various performances. More preferably, it is the range of 0.4-1.3 equivalent. Moreover, it is preferable that this hardened | cured material layer is 0.3-10 micrometers in thickness, More preferably, it is 0.5-5 micrometers.

  A curing catalyst can be added as necessary when the above-mentioned hydroxyl group-containing acrylic resin and a curable resin containing a polyisocyanate compound are reaction-cured. Specific examples of the curing catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3. 0.0] nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanol Amine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxy Silane, 3- (2-aminoethyl) amino Various amine compounds such as propyltrimethoxysilane and 3- (2-aminoethyl) aminopropylmethyldimethoxysilane; tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxylpropyl) ammonium salt, cyclohexyltrimethylammonium salt Various quaternary ammonium salts such as tetrakis (hydroxylmethyl) ammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, o-trifluoromethylphenyltrimethylammonium salt, and representative counter anions So-called quaternary ammonium salts, dibutyltin dilaurate, dibutyltin acetate, geol, having chloride, bromide, carboxylate, hydroxide, etc. Chill lead, such as cobalt naphthenate, there are various organic metal compounds such as. Furthermore, the cured product layer may contain a colorant in order to impart design properties.

  In the cured product layer used in the laminated sheet for molding of the present invention, polypropylene, polyethylene, an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA) for the purpose of making it difficult to cause cracks during stretching, if necessary. , Polyisobutylene, polybutadiene, polystyrene, polycarbonate, polymethylpentene, ionomer, acrylonitrile-butadiene-styrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, polyvinyl alcohol, polyamide resin, polyacetal, polyester, modified polyphenylene ether, alkyd resin Various thermoplastic resins such as silicon resin and fluorine resin may be blended.

  In the cured product layer used in the laminated sheet for molding of the present invention, if necessary, defoaming, fluidity modification, anti-blocking, anti-static, anti-oxidation in the resin, as long as the designability and stretchability are not impaired. Various additives used in conventional paints and the like can be used for the purposes of 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.

  The cured product layer is formed by a step of printing or coating a curable resin on a transparent or translucent thermoplastic acrylic resin film and a step of semi-curing the resulting coating film at a temperature of 50 ° C. or lower. be able to. For example, in the semi-curing step, it is preferably maintained at 40 to 50 ° C. for 3 to 4 days. Printing or coating methods include gravure printing, flexographic printing, screen printing, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, kiss touch reverse coater. In addition, a coating method such as a comma coater, a comma reverse coater, or a micro gravure coater can be used.

(Thermoplastic resin layer)
The laminated sheet for molding of the present invention may have a transparent or translucent thermoplastic resin layer 4 as a layer for forming the surface layer of the molded body as shown in FIG. The thermoplastic resin is preferably an acrylic resin film or a fluorine-based film that is excellent in terms of integral moldability at low temperatures of about 100 to 200 ° C. and weather resistance. When the molding temperature is 200 ° C. or higher, the metallic luster layer is deteriorated by heat and the design properties are lowered. In order to perform a molding process by heat such as vacuum molding, the acrylic resin film is a single layer or multilayer film having a softening point in the range of 60 to 300 ° C, preferably 70 to 220 ° C, more preferably 80 to 190 ° C. Preferably there is. The film may contain a colorant. The film thickness of the film layer can be appropriately selected as necessary. For example, the thickness is 50 to 300 μm, preferably 70 to 150 μm.

(Supporting substrate layer)
As shown in FIG. 4, the laminated sheet for molding of the present invention may be provided with a support base material layer 7 made of a thermoplastic resin on the back surface of the decorative layer.

  As the support base material layer, a sheet mainly composed of a thermoplastic resin is used in order to perform a heat forming process such as vacuum forming. Further, when the obtained laminated sheet for molding is used for injection molding after vacuum molding or the like, it is preferable to select a thermoplastic resin base sheet having adhesiveness to the resin to be injection molded.

  For these reasons, examples of the supporting resin layer include acrylonitrile / butadiene / styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, and polyethylene (PE). General-purpose resins such as resins, polypropylene (PP) resins, vinyl chloride (PVC) resins, olefin elastomers (TPO), vinyl chloride elastomers (TPVC), styrene elastomers (SBC), urethane elastomers (TPU) Thermoplastic elastomers (TPE) such as polyester 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. The support base material layer may be composed of a plurality of layers.

(Adhesive layer)
The method of laminating the supporting base material layer selected from the various resin sheets described above on the printed or coated decorative layer is the interface between the metallic luster layer 2 and the supporting base material layer 7 as shown in FIG. A method using an adhesive as the adhesive layer 6 or a method using no adhesive may be used. 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 room temperature to about 60 ° C. may be used as the binder resin for the metallic luster layer.

  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.

(Printing or coating method)
The metallic gloss layer and the adhesive printing or coating method of the laminated sheet for molding of the present invention include gravure printing, flexographic printing, screen printing and other printing methods, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater. Coating methods such as a knife coater, an air knife coater, a kiss touch coater, a kiss touch reverse coater, a comma coater, a comma reverse coater, and a micro gravure coater can be used.

  In the laminated sheet for molding of the present invention, on the surface layer side (surface side of the colored layer) at the time of molding, design properties, friction resistance, scratch resistance, weather resistance, stain resistance, water resistance, chemical resistance and In order to impart performance such as heat resistance, one or more transparent, semi-transparent or colored clear top coat layers can 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.

  The molding laminated sheet of the present invention can be used as a surface layer in various molding methods. For example, a laminated sheet for molding is placed with a transparent or translucent thermoplastic acrylic resin film on the surface side, and a preform having a three-dimensional shape is formed by thermoforming, and then placed in an injection mold. It can be molded by an insert injection molding method that inserts and integrates with an injection resin. 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, a portion having a high degree of stretching can also maintain a design appearance, that is, a deep appearance.

  In order to maintain a high metallic luster after molding, thermoforming at a low temperature is preferable, and for that purpose, a match mold forming method using a match mold formed of a pair of male and female dies is preferable. According to this molding method, since the metallic luster layer has a high glossiness even after molding, the obtained molded product has a sense of depth.

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%.
(Evaluation of cracks)
In the present invention, the stretchability is defined as follows from the viewpoint of crack resistance, with the crack on the appearance of the sheet after molding as a criterion. The forming process is performed at a temperature higher than the softening point of the material constituting the forming laminated sheet (for example, a sheet temperature of about 100 to 170 ° C.). Thereafter, the thickness of the laminated sheet for molding is measured, and the portion having a thickness of 100 / n (the portion that is stretched to have an area of n / 100 times) is stretched by n% with respect to the thickness before the molding process. It is called a part, and it is visually judged whether or not a crack has occurred in that part, and the one that has cracked is (X), the one that has not been cracked (O), but the crack cannot be judged visually, but it is 200 to 500 times (△) indicates that micro cracks are observed when observed with a microscope. When such a crack occurs, the gloss value of the metallic luster layer decreases, and it becomes difficult to obtain depth.

(Extensible)
The stretchability of the molding laminated sheet of the present invention is, after stretching, 100/130 times in thickness, that is, a portion where the area becomes 1.3 times (130% stretched portion), 100/150 times in thickness, that is, area. The cracking state of the sheet was observed in each of the stretched portions of the portion where the thickness was 1.5 times (150% stretched portion) and the thickness was 100/200 times, that is, the portion where the area was 2.0 times (200% stretched portion) Then, the pass / fail was evaluated with (Δ) as a pass. Similarly, gloss values were measured for stretched portions of 130%, 150%, and 200%.

(Production method)
(No cured product layer)
The laminated sheet for molding of the present invention is
1) a step of applying a color layer on a thermoplastic resin layer or a release film;
2) forming a metallic luster layer having a specular metallic luster by vapor deposition on the colored layer or printing a gravure ink containing a metal thin film strip and a binder resin;
Can be manufactured.

(With cured product layer)
The laminated sheet for molding of the present invention having a cured product layer is
1) a step of applying a color layer on a thermoplastic resin layer or a release film;
2) A step of applying a curable resin composition containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound on the color layer;
3) forming a semi-cured cured product layer by semi-curing the resulting coating film at a temperature of 50 ° C. or less;
4) forming a metallic luster layer having a mirror-like metallic luster by depositing a metal on the obtained cured product layer or printing a gravure ink containing a metal thin film strip and a binder resin. It can be manufactured by a manufacturing method.

  The laminated sheet for molding of the present invention provides a molded product having a design having a stretchability necessary for molding by vacuum molding or the like and a good depth feeling. After thermoforming, it can be used for automobile members, home appliance members, building members and the like as plastic molded bodies decorated by in-mold injection molding.

(Measurement of lightness and saturation)
The saturation of the reflected light is measured using a variable angle spectrocolorimetry system GCMS-4 (manufactured by Murakami Color Research Laboratory) as a measuring instrument under the conditions of 45 ° illumination and 45 ° light reception, and the color values (L ^* , a ^*). , B ^* , C ^* ).

The brightness of the transmitted light is measured with a spectral colorimeter CM-3500d (manufactured by Konica Minolta Co., Ltd.) according to JIS Z 8722 “Color measurement method: reflection and transmission object color” with a D65 light source and a 10-degree field of view. Measured and determined from color values (L ^* , a ^* , b ^* , C ^* ).
The color values (L ^* , a ^* , b ^* , C ^* ) are in accordance with JIS Z 8729 “Color display method-L ^* a ^* b ^* color system and L ^* u ^* v ^* color system”. It is specified.

(Gloss value measurement method)
In the present invention, the gloss value of the metallic gloss layer is the gloss value of the metallic gloss layer formed on the transparent or translucent thermoplastic acrylic resin film, and gloss meter: micro-TRI-gloss (by BYK Gardner) ) From the side of the transparent or translucent thermoplastic acrylic resin film, under the condition of 20 ° / 20 °.
Also, the change rate of the surface gloss value is
Change rate of surface gloss value = (Gloss value of non-stretched portion−Gloss value of stretched portion) ÷ (Gloss value of non-stretched portion) × 100 (%)
Define in.
In the present invention, a sheet having a gloss change rate of 30% or less, preferably a sheet having 25% or less is preferable in each of 130% stretching, 150% stretching, and 200% stretching.
(Reaction rate of cured product layer)
The reaction rate of the cured product layer was measured by measuring the absorbance of the isocyanate functional group with an infrared spectrophotometer FT-IR 460PLUS manufactured by JASCO Corporation.

  For the molding process, a trapezoidal test mold having a square with a top surface of 5 cm on one side, a square with a bottom surface of 7 cm on one side and a ridge of 2 cm is used, and the top surface portion is stretched by 130%, 150% and 200%. Thus, the sheet holding position was changed, and the vacuum forming method was performed under the conditions of a sheet temperature of 155 ° C. and a mold temperature of 60 to 80 ° C.

(Deepness evaluation method)
Ten evaluators performed a two-level sensory test to determine whether or not they feel a sense of depth. Seven or more evaluators felt that they felt a sense of depth. None ”.

The sample for evaluation was manufactured as follows.
(1) High glitter ink Aluminum thin film slurry (nonvolatile content 10%) 30 parts Binder resin Carboxylic acid-containing vinyl chloride-vinyl acetate resin 3 parts
("Vinylite VMCH" manufactured by UCC)
Urethane resin
(Arakawa Chemical "polyurethane 2593" non-volatile content 32%) 8 parts ethyl acetate 23 parts methyl ethyl ketone 26 parts isopropanol 10 parts The above was mixed to prepare a high-gloss ink having a concentration of 35% by mass of aluminum thin film in the non-volatile content. .
(1-1) 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 so that the thickness is 0.025 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 case of the release layer. It was applied to form a coat layer.

  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.

(1-2) 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.
(1-3) Preparation of high gloss ink Aluminum thin film slurry (nonvolatile content 10%) 30 parts Binder Resin Carboxylic acid-containing vinyl acetate resin 3 parts
("Vinylite VMCH" manufactured by UCC)
Urethane resin
(Arakawa Chemical "polyurethane 2593" non-volatile content 32%) 8 parts ethyl acetate 23 parts methyl ethyl ketone 26 parts isopropanol 10 parts The above was mixed to prepare a high-gloss ink having a concentration of 35% by mass of aluminum thin film in the non-volatile content. .

(2) Hardened material layer Below, the synthesis example of the hydroxyl-containing acrylic resin used for a hardened | cured material layer is shown. A weight average molecular weight shows the polystyrene conversion value of a GPC measurement result. The solid content was obtained by taking 1 g of a sample in an aluminum dish, spreading it thinly and uniformly with toluene, air drying, further drying in a hot air dryer at 108 ° C. for 1 hour, and calculating from the mass after drying. The hydroxyl value was calculated from the monomer charge composition as the KOH neutralization amount, the polymer Tg was measured by DSC, and the acid value was measured by 0.05 mol · dm-3 potassium hydroxide-toluene solution titration method.

(2-1) Synthesis example 1 of hydroxyl group-containing acrylic resin
850 parts of butyl acetate and 1 part of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) are added to a reaction vessel equipped with a temperature controller, a nitrogen introducing tube, a dropping device (2 units), and a stirring device. After charging and nitrogen substitution, the temperature was raised to 110 ° C. over 1.5 hours.

  Separately, 660 parts of methyl methacrylate, 150 parts of t-butyl methacrylate and 190 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as monomer solution 1), 200 parts of isobutyl acetate and perbutyl O (trade name, Nippon Oil & Fats Co., Ltd.) A solution in which 9 parts of t-butyl peroxy-2-ethylhexanoate manufactured by the company and 2 parts of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) are mixed well (hereinafter referred to as catalyst solution). 1), each was charged into a dropping device and immediately purged with nitrogen.

  The monomer solution 1 and the catalyst solution 1 were dropped into the reaction vessel under a nitrogen atmosphere over 5 hours while monitoring the reaction temperature so as not to increase rapidly. As a result of continuing stirring for about 15 hours after the completion of dropping, a resin composition (O-1) having a solid content of 60% was obtained. The weight average molecular weight of the obtained resin was 100,000, the hydroxyl value of the solid content was 79, and Tg was 95 ° C.

(2-2) Synthesis example 2 of hydroxyl group-containing acrylic resin
850 parts of butyl acetate and 1 part of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) are added to a reaction vessel equipped with a temperature controller, a nitrogen introducing tube, a dropping device (2 units), and a stirring device. After charging and replacing with nitrogen, the temperature was raised to 110 ° C. over 1.5 hours with stirring.

  Separately, a solution in which 650 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, 40 parts of 2-ethylhexyl methacrylate, 165 parts of 2-hydroxyethyl acrylate, 40 parts of allyl methacrylate, and 5 parts of methacrylic acid were mixed well (hereinafter referred to as monomer solution 2 and ) And 200 parts of isobutyl acetate, 11 parts of perbutyl O (trade name, manufactured by Nippon Oil & Fats Co., Ltd., t-butylperoxy-2-ethylhexanoate), perbutyl Z (trade name, manufactured by Nippon Oils and Fats Co., Ltd., t -Butyl peroxybenzoate) A solution in which 2 parts were mixed well (hereinafter referred to as catalyst solution 2) was charged in a dropping device and immediately purged with nitrogen.

  The above monomer solution 2 and catalyst solution 2 were added dropwise to the reaction vessel under a nitrogen atmosphere over 5 hours while monitoring the reaction temperature so as not to increase rapidly. As a result of continuing stirring for about 15 hours after the completion of dropping, a resin composition (O-2) having a solid content of 51% was obtained. The weight average molecular weight of the obtained resin was 16,800, the hydroxyl value of the solid content was 72, and Tg was 72 ° C.

(2-3) Polyisocyanate Compound As the polyisocyanate compound in the present invention, “BURNOCK DN-980” (trade name, manufactured by Dainippon Ink & Chemicals, Inc., isocyanurate ring-containing polyisocyanate, number average molecular weight 800, nonvolatile content 75 % (Solvent: ethyl acetate), number of functional groups 3, NCO concentration 15%; hereinafter referred to as DN-980).

The said hydroxyl-containing acrylic resin (O-1-2) and a polyisocyanate compound are mix | blended and mixed by a predetermined ratio, and the cured | curing material of the semi-hardened state of curable resin containing a hydroxyl-containing acrylic resin and a polyisocyanate compound is mixed. A working solution was prepared. A cured product layer is formed from this solution or a coating solution containing this solution.

(3) Color layer (3-1) Color layer solution-1
Microlith K (manufactured by Ciba Specialty) Blue-4GK 35 parts Univia A transparent medium (manufactured by Dainippon Ink) 35 parts UR-2 medium (manufactured by Dainippon Ink) 30 parts Was prepared.
The average particle size of Microlith K Blue-4GK was 123 nm.

(3-2) Color layer solution-2
Microlith K (manufactured by Ciba Specialty) Red-4CK 25 parts The hydroxyl group-containing acrylic resin O-1 41 parts BORNOCK DN-980 (Dainippon Ink Co., Ltd.) 10 parts Ethyl acetate 112 parts Butyl acetate 112 parts A color layer solution-2 was prepared.
The average particle size of Microlith K Red-4CK was 160 nm.

(3-3) Color layer solution-3
Microlith K (manufactured by Ciba Specialty) Yellow-3GK
25 parts hydroxyl group-containing acrylic resin O-1 41 parts BORNOCK DN-980 (Dainippon Ink Co., Ltd.) 10 parts ethyl acetate 112 parts butyl acetate 112 parts The above was mixed to prepare Color Layer Solution-3.
The average particle size of Microlith K Yellow-3GK was 854 nm.

(4) 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 was obtained.

As a thermoplastic acrylic resin layer, transparent, transmitted light brightness L ^* = 93, a rubber-modified PMMA film (hereinafter referred to as film A) having a thickness of 125 μm, and as a supporting base layer, gray, opaque, having a thickness of 300 μm An ABS film (hereinafter referred to as film C) was used.
(Examples 1-4, Reference Examples 1-3, Comparative Example 1)

(Example 1)
The layer configuration was film A / color layer-1 / metallic gloss ink / adhesive / film C. On the film A, the color layer solution-1 was applied with a gravure coater to a dry film thickness of 2.0 μm and dried. The lightness L ^* (PL ^* ) of the transmitted light of the colored layer (film A / color layer-1) thus formed was determined by the above measurement method.

Further, a metallic gloss ink was applied onto color layer-1 of film A with a gravure coater to a dry film thickness of 2.0 μm and dried. An adhesive was applied onto the obtained metallic gloss layer with a gravure coater at a dry coating amount of 5.0 g / m ² , and immediately bonded to the film C. Aged for days. Then, it shape | molded by the vacuum forming method and obtained the molded object.
(Reference Example-1)
The layer structure was film A / metallic gloss ink / adhesive / film C, and a laminated sheet for molding was prepared in the same manner as in Example 1 except for the color layer. The gloss value was measured from the film A side by the above method. The gloss value measured was 500.
(Example 2)
The layer configuration was film A / color layer-1 / deposition layer / adhesive / film C. Color layer solution-1 was applied to a dry film thickness of 2.0 μm with a gravure coater and dried. The lightness L ^* (PL ^* ) of the transmitted light of the colored layer (film A / color layer-1) thus formed was determined by the above measurement method.

On the obtained colored layer, aluminum was vapor-deposited on the film A so as to have a thickness of 40 nm at a vacuum degree of 10 ⁻⁴ TOLL or less using a ULVAC EBX-6D vacuum vapor deposition machine manufactured by ULVAC. Further, an adhesive was coated thereon with a gravure coater at a dry coating amount of 5.0 g / m ² , and immediately bonded to the film C. The obtained laminated sheet for aging was aged at 40 ° C. for 3 days. Then, it shape | molded by the vacuum forming method and obtained the molded object.

(Reference Example-2)
The layer structure was film A / deposition layer / adhesive / film C, and a laminated sheet for molding was prepared in the same manner as in Example 2 except for the color layer. The gloss value was measured from the film A side by the above method. The gloss value measured was 1600.

(Examples 3 and 4)
The layer configuration was film A / color layer-2 / cured product layer / metallic gloss ink / adhesive / film C. Color layer solution-2 was applied onto film A with a gravure coater to a dry film thickness of 2.0 μm and dried. The lightness L ^* (PL ^* ) of the transmitted light of the colored layer thus formed (film A / color layer-2) was determined by the above measurement method.

A curable resin composition was blended in the ratio shown in Table 1 for the cured product layer, and the resulting solution was applied onto color layer-2 of film A so as to have a dry film thickness of 2.0 μm with a microgravure coater. And aged at 50 ° C. for 4 days. The lightness L ^* (PL ^* ) of the transmitted light of the colored layer thus formed (film A / color layer-2 / cured product layer) was determined by the above measurement method.

Further, a metallic gloss ink was applied on the cured product layer formed on the film A with a gravure coater to a dry film thickness of 2.0 μm and dried. The adhesive was applied with a gravure coater to a dry coating amount of 5.0 g / m ² and immediately bonded to film C, and the resulting laminated sheet was aged at 40 ° C. for 3 days. Then, it shape | molded by the vacuum forming method and obtained the molded object. The reaction rate of the cured product layer was determined by applying an infrared spectrophotometer on the film A after blending and mixing the solution shown in Table 1 to a dry film thickness of 2.0 μm and aging at 40 ° C. for 3 days. Measured with

表１中、Ｎ／Ｏ比は、硬化性樹脂組成物に含有される水酸基含有アクリル系樹脂中の水酸基１当量当たりの、ポリイソシアネート化合物中のイソシアネート基の当量を示す。
（参考例−３、４）
層構成を、フィルムＡ／硬化物層／金属光沢インキ／接着剤／フィルムＣとし、色層以外は実施例３、４と同様にして成形用積層シートを作成した。フィルムＡ側から上記の方法で光沢値を測定した。測定した光沢値は８００、８１０であった。

In Table 1, N / O ratio shows the equivalent of the isocyanate group in the polyisocyanate compound per equivalent of hydroxyl group in the hydroxyl group-containing acrylic resin contained in the curable resin composition.
(Reference examples -3, 4)
The layer structure was film A / cured material layer / metallic gloss ink / adhesive / film C, and a laminated sheet for molding was prepared in the same manner as in Examples 3 and 4 except for the color layer. The gloss value was measured from the film A side by the above method. The measured gloss values were 800 and 810.

(Comparative Example 1)
Comparative Example 1 was prepared in the same manner except that Color Layer-2 was changed to Color Layer-3 in Example 3, and then molded by a vacuum molding method.
(Comparative Example 2)
Comparative Example 2 was prepared in the same manner as in Example 3 except that the cured product layer was changed to the composition for Comparative Example 2 in Table 1 in Example 3, and then molded by a vacuum molding method.
(Reference Example-5)
The layer configuration was film A / cured product layer / metallic gloss ink / adhesive / film C, and a laminated sheet for molding was prepared in the same manner as in Comparative Example 2 except for the color layer. The gloss value was measured from the film A side by the above method. The gloss value measured was 160.

Table 2 shows the feeling of depth of the laminated sheet for molding of the present invention and the feeling of depth of the molded article formed from the laminated sheet for molding.

表２において、
ＰＬ^＊：透過光の明度Ｌ^＊
ＲＣ^＊：４５°反射光の明度Ｃ^＊
なし＊：金属光沢面に著しい割れが生じ、意匠を損なった。

In Table 2,
PL ^* : Lightness L ^{* of} transmitted light
RC ^* : 45 ° reflected light brightness C ^*
None *: Remarkable cracks occurred on the glossy metallic surface, and the design was damaged.

Table 3 shows the gloss value of the laminate sheet for molding having the metallic gloss layer constituting the laminate sheet for molding of the present invention and the gloss value of the molded body obtained by thermoforming the sheet.

  The gloss of the 150% and 200% stretched products of Reference Example 2 was not measurable due to significant cracking on the glossy metallic surface.

All of the molded products of the examples had a good depth feeling and a beautiful design, but the molded products of the comparative examples had no depth and a design with no sense of depth.

  According to the present invention, it has an initial appearance with a good depth feeling, stretchability required at the time of molding, that is, crack resistance against stretching by a heating vacuum molding method, and good depth feeling after molding. It is possible to provide a laminated sheet for molding that can provide a design having a certain appearance and can obtain a sufficient surface hardness without a post-curing step.

FIG. 2 is a schematic view of a molding laminated sheet of the present invention, which has a colored layer (= color layer) and a metallic luster layer. FIG. 2 is a schematic view of a laminated sheet for molding of the present invention, which has a colored layer (= thermoplastic resin layer + color layer) and a metallic luster layer. FIG. 2 is a schematic view of a laminated sheet for molding according to the present invention, which has a colored layer (= thermoplastic resin layer + color layer + cured material layer) and a metallic luster layer. FIG. 2 is a schematic diagram of a laminated sheet for molding according to the present invention, which includes a colored layer (= thermoplastic resin layer + color layer + cured material layer), a metallic luster layer, an adhesive layer, and a supporting base material layer. is there.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color layer 2 Metal luster layer 3 Colored layer 4 Thermoplastic resin layer 5 Cured material layer 6 Adhesive layer 7 Support base material layer

Claims (12)

In a laminated sheet for colored molding in which a transparent or translucent colored layer and a metallic gloss layer having metallic luster are laminated in this order from the surface layer side,
a) The lightness L ^* of the transmitted light of the colored layer is 20 to 80,
b) The gloss value of the metallic luster layer is 200 or more,
c) A laminated sheet for molding having a chroma C ^* of regular reflection light of 45 ° on the surface side of the laminated sheet for molding of 150 or more. The laminated sheet for molding according to claim 1, wherein the colored layer has a laminated structure of a transparent or translucent thermoplastic resin layer and a transparent or translucent color layer. The molded laminated sheet according to claim 1, wherein the colored layer has a laminated structure of a transparent or translucent thermoplastic resin layer, a transparent or translucent color layer, and a transparent or translucent cured product layer. The laminated sheet for molding according to claim 3, wherein the cured product layer is a semi-cured cured product of a transparent or translucent curable resin containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound. The molded laminated sheet according to any one of claims 1 to 4, wherein the colored layer has a colored layer in which a semi-cured cured product of a curable resin containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound is colored. . The laminated sheet for molding according to any one of claims 1 to 5, wherein the metallic luster layer is a layer containing a metal thin film strip and a binder resin. The laminated sheet for molding according to claim 1, wherein the gloss value of the metallic gloss layer is 400 or more. The laminated sheet for molding according to claim 1, wherein the colored layer contains a pigment having an average particle diameter of 200 nm or less. The hydroxyl group-containing acrylic resin has a glass transition temperature of 70 to 120 ° C., a hydroxyl value of 10 to 100, and a weight average molecular weight of 10,000 to 200,000, and the polyisocyanate compound is a hydroxyl group 1 in the hydroxyl group-containing acrylic resin. The laminated sheet for molding according to claim 4, which has 0.3 to 2.0 equivalents of isocyanate groups per equivalent. The laminated sheet for molding according to claim 1, wherein a supporting base material layer composed of a thermoplastic resin is provided on the back surface of the metallic gloss layer. The molded object obtained by thermoforming the laminated sheet for shaping | molding of Claims 1-10. The molded body according to claim 11, wherein the thermoforming is a match mold molding method.

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