JP2004050786A - Lustrous sheet, lustrous resin molding, and method of manufacturing lustrous resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lustrous sheet which can be integrally molded by thermoforming such as vacuum molding or injection molding and can provide an injection molding having excellent metallic luster and impact resistance, to provide a lustrous resin molding provided with a lustrous surface layer part having excellent metallic luster, impact resistance, and a unique metallic color tone created by superposition of colors through a plurality of layers, and to provide a method of manufacturing a lustrous resin molding having a lustrous surface layer part having excellent metallic luster and impact resistance. <P>SOLUTION: This lustrous sheet is provided with a lustrous layer formed of a resin composition containing a lustrous glass flake, covered with at least one member selected from the group consisting of a metal and a metal oxide, and a thermoplastic resin, and has a thermal contraction stress of 0.1 to 1 MPa in each of a longitudinal stretching direction and a transverse stretching direction. In addition to the lustrous layer, a colored layer or the like, which can be seen through the lustrous surface layer part, is further provided. <P>COPYRIGHT: (C)2004,JPO

Description

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【発明の効果】
本発明の光輝性シートは、金属及び金属酸化物から成る群から選ばれる少なくとも１種で被覆された光輝性ガラスフレークと熱可塑性樹脂とを含有する樹脂組成物で構成される光輝性層を有し、縦延伸方向と横延伸方向の熱収縮応力が各々０．１〜１ＭＰａの弱延伸を施した光輝性シートであるために、優れた金属光沢を維持したまま、熱成形や射出成形により一体成形することができる。
着色層上に光輝性層を設けた光輝性シートは、光輝性層から着色層と基材層の少なくとも１種を透視できることにより、独特の金属色調と意匠性を発現する。また、光輝性層の上にクリヤー層を設けた光輝性シートは、クリヤー層により光輝性層中に含まれるガラスフレークの形状による表面への凹凸の影響を緩和でき、表面平滑度を高めることができるため、一層優れた金属光沢を発現する。
本発明の光輝性樹脂成形品は、光輝性表層部として金属及び金属酸化物から成る群から選ばれる少なくとも１種で被覆された光輝性ガラスフレークと熱可塑性樹脂とを含有する樹脂組成物で構成される光輝性層と光輝性層の裏面に設けられた着色層とを有し、前記光輝性層の表面側から前記着色層の少なくとも一部を透視し得るために、優れた金属光沢、独特の金属色調および耐衝撃性を有し、自動車、二輪車、ＯＡ機器および家電製品等の内外装部材などに好適に用いられる。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a glittering sheet that can be injection-molded and useful as an interior / exterior member of an automobile or a home appliance, a glittering resin molded product using the glittering sheet, and a method for producing the glittering resin molded product.
[0002]
[Prior art]
Conventionally, a resin molded product having a metallic luster is obtained by applying a thermosetting resin paint containing a glittering material such as mica or metal powder to a surface of a molded body manufactured by injection molding or the like and heat-curing. . However, this manufacturing method involves many steps, is costly, and has an environmental problem that a large amount of volatile solvent is discharged during coating.
[0003]
As a means to solve these problems, attempts have been made to mix thermoplastic resin with a glittering material and injection molding, but mica, metal powder, aluminum flake, etc., which are widely used as glittering materials, have been used for thermoplastic resin. When these materials are added and kneaded, these glittering materials are crushed and deformed during kneading, and their glittering properties are greatly reduced (Japanese Patent Laid-Open No. 4-359937). For this reason, in order to give a molded product excellent metallic luster, it is necessary to mix a large amount of expensive brilliant material into a thermoplastic resin. There has been a problem that the original mechanical strength of the plastic resin is impaired.
[0004]
It has long been practiced to mix glittering glass flakes coated with metal into paint resins, and there have been many reports on this, while there are very few examples of kneading in thermoplastic resins. No. 3,599,937 describes that an injection-molded product of a kneaded product of a metal-coated glass flake and a thermoplastic resin has a high-grade metallic luster, and that a metal-coated glass flake is used as an injection-molded product. It is reported to have favorable mechanical strength. However, heretofore, no examples have been reported in which glass flakes coated with metal are used for stretched sheets.
[0005]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a glitter sheet that can be integrally molded by thermoforming such as vacuum molding or injection molding and that provides an injection-molded article having excellent metallic luster and impact resistance. is there.
Another object of the present invention is to provide a brilliant resin molded article having a brilliant surface layer having a unique metallic color due to excellent metallic luster and impact resistance and overlapping colors through a plurality of layers. It is in.
Another object of the present invention is to provide a method for producing a glitter resin molded article having a glitter surface layer having excellent metallic luster and impact resistance.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found the following findings.
(1) A glittering sheet comprising a glittering glass flake (hereinafter abbreviated as a glittering glass flake) coated with at least one member selected from the group consisting of metals and metal oxides and a resin composition of a thermoplastic resin, Impact resistance, especially at low temperatures, was insufficient. However, when the glitter sheet is stretched under normal stretching conditions for the purpose of improving impact resistance and moldability, voids are generated due to peeling at the interface between the glitter glass flakes and the thermoplastic resin, and the resulting glitter property is increased. The metallic luster of the sheet is significantly reduced. Therefore, the brilliancy is determined in a stretching condition of 1.1 to 2 times, which is a stretching condition under which the interface separation between the brilliant glass flake and the thermoplastic resin does not occur, and which is a stretching condition capable of satisfying impact resistance and moldability. By stretching the sheet and applying a heat shrinkage stress of 0.1 to 1 MPa, a glittering sheet that can be integrally formed by thermoforming such as vacuum forming or injection molding, and has excellent impact resistance and metallic luster. To be obtained.
(2) At least one of a glitter layer composed of a resin composition composed of a glitter glass flake and a thermoplastic resin, a colored layer composed of a resin composition composed of a colorant and a thermoplastic resin, and a base layer. A brilliant resin molded article having at least one of a colored layer and a base layer that can be seen through the surface of the brilliant layer, has an excellent metallic luster and a unique metallic color tone due to the multilayer color overlap.
The present invention has been completed based on the above findings.
[0007]
That is, the present invention has a glittering layer composed of a resin composition containing a glittering glass flake and a thermoplastic resin coated with at least one selected from the group consisting of metals and metal oxides, Provided is a glitter sheet, wherein heat shrinkage stresses in a longitudinal stretching direction and a transverse stretching direction are each 0.1 to 1 MPa.
[0008]
Further, the present invention is a resin molded product in which a glitter surface layer portion and a main body portion formed of a thermoplastic resin provided on the back surface of the glitter surface layer portion are integrally formed, wherein the glitter surface layer portion is A glitter layer formed of a resin composition containing a glitter glass flake coated with at least one selected from the group consisting of a metal and a metal oxide and a thermoplastic resin, and a glitter layer provided on the back surface of the glitter layer A colored layer composed of a resin composition containing a coloring agent and a thermoplastic resin, wherein at least a part of the colored layer can be seen through from the surface side of the glittering layer. Provide a glittering resin molded product.
[0009]
Further, the present invention has a glittering layer composed of a resin composition containing a glittering glass flake and a thermoplastic resin coated with at least one selected from the group consisting of metals and metal oxides, The glitter sheet having a heat shrinkage stress in the longitudinal stretching direction and the transverse stretching direction of 0.1 to 1 MPa, respectively, is disposed in a metal mold so that the glitter layer of the preformed body is in contact with the female mold. The present invention provides a method for producing a brilliant resin molded product, which comprises integrally molding a thermoplastic resin or a preform thereof by injection molding a thermoplastic resin on the back surface thereof.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Glitter generally used widely, for example, luster pigment such as mica or brass powder, metal powder having a smooth surface such as aluminum powder, scaly glitter material such as aluminum flakes is added to thermoplastic resin and melt-kneaded. Due to the strong shearing force applied during kneading, these glittering materials are crushed and deformed, and their glittering properties are greatly reduced. In the glittering sheet of the present invention, glittering glass flakes (hereinafter referred to as glittering glass flakes) coated with at least one selected from the group consisting of metals and metal oxides having excellent mechanical strength are used as glittering materials. By using the same, it is possible to prevent the brilliant material from being broken and deformed at the time of melt-kneading with the thermoplastic resin.
[0011]
The material of the base glass of the glittering glass flakes used for the glittering sheet of the present invention may be glass flake glass used for paints, and is not particularly limited, but silicate glass, silicate acrylic glass, soda-lime glass, and lead glass And the like. At least one coating selected from the group consisting of metals and metal oxides used to impart a metallic luster to glass flakes is gold, silver, platinum, palladium, nickel, copper, aluminum, chromium, brass, tin. And metal alloys such as Hastelloy and silver tin alloys, and metal oxides such as titanium oxide. The base glass surface is coated by a method such as electroless plating and sputtering.
Among these metals, those using silver, hastelloy, brass or titanium oxide are preferably used because they are inexpensive and have good metallic luster.
[0012]
In order to obtain excellent metallic luster and smoothness of the sheet surface, it is preferable that the glittering glass flakes used have an average particle size of 10 to 150 μm and an average thickness of 1 to 10 μm. When the average particle size is less than 10 μm, the glitter is inferior and good metallic luster is hardly obtained. When the average particle size exceeds 150 μm, the unevenness of the sheet surface becomes large and the smoothness of the sheet cannot be obtained. Further, those having an average thickness of more than 10 μm are not preferred because of their low glitter.
[0013]
The amount of the brilliant glass flakes added to 100 parts by mass of the thermoplastic resin in the resin composition containing the brilliant glass flakes and the thermoplastic resin constituting the brilliant layer is such that a sufficient metallic luster is obtained, and The amount is preferably from 0.1 to 6 parts by mass, which does not reduce the mechanical properties of the resin, and more preferably from 0.5 to 3 parts by mass. If the amount is less than 0.1 part by mass, the density of the glittering glass flake is low, and good metallic luster cannot be obtained. On the other hand, if it is added in excess of 6 parts by mass, the mechanical properties of the resin composition tend to decrease, and the transparency of the resin composition also decreases, resulting in a glittering layer having a total light transmittance of 20% or more. Is difficult to obtain.
[0014]
The thermoplastic resin in the resin composition constituting the glittering layer is not particularly limited, but preferably has excellent weather resistance and mechanical strength. For example, acrylonitrile-butadiene-styrene copolymer (ABS) Rubber-containing thermoplastic resins such as acrylonitrile-acrylic rubber-styrene copolymer (AAS) and acrylonitrile-ethylene rubber-styrene (AES) copolymer, acrylonitrile-styrene copolymer (AS), acrylic resin, Examples include polystyrene, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate. Above all, in the case of a glittering sheet provided with a coloring layer or a base layer described below on the back surface of the glittering layer, it is excellent in design that the color of the coloring layer or the base layer can be seen through from the surface side of the glittering layer. For this reason, a transparent resin such as an acrylic resin, polystyrene, AS, AES, or AAS is preferably used. Further, a thermoplastic acrylic resin is particularly preferable from the viewpoint of excellent interlayer adhesion with a colored layer or a clear layer described later and durability of a molded product.
[0015]
Examples of the thermoplastic acrylic resin include, for example, homopolymers such as (meth) acrylic acid, (meth) acrylate, acrylonitrile, and methacrylonitrile, and copolymers containing these as a main component. Are poly (methyl meth) acrylate, methyl methacrylate-methyl acrylate copolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-ethyl methacrylate copolymer, polyacrylonitrile, acrylonitrile-styrene copolymer Polymers, acrylonitrile-methyl methacrylate copolymer, and the like are included. Among them, a homopolymer of methyl methacrylate or acrylonitrile, or a copolymer containing these as a main component, is particularly preferable in terms of excellent weather resistance, ultraviolet shielding property, and transparency.
[0016]
The glittering sheet of the present invention is a glittering layer composed of a resin composition containing a glittering glass flake coated with at least one selected from the group consisting of the above-mentioned metals and metal oxides, and a thermoplastic resin. However, the impact resistance is reduced due to the inclusion of the glitter glass flakes, and in order to obtain sufficient impact resistance as the glitter sheet, the glitter sheet is subjected to a stretching treatment. Is preferred.
However, when a glitter sheet made of a resin composition of a glitter glass flake and a thermoplastic resin is stretched at a normal stretching ratio, a void is generated at the interface between the glitter glass flake and the thermoplastic resin due to peeling, and the resulting glitter is obtained. It was found that the metallic gloss of the conductive sheet was significantly reduced.
[0017]
The present inventors have studied the relationship between the stretching ratio and the occurrence of peeling of a glittering sheet having a glittering layer comprising a glittering glass flake and a resin composition of a thermoplastic resin. As a result, the stretching ratio was 2.0 times or less. If it is, it has been found that a good metallic luster that does not cause peeling at the interface between the glittering glass flake and the thermoplastic resin can be obtained.
[0018]
In addition, in order to achieve both impact resistance and moldability of a glittering sheet having a glittering layer composed of a glittering glass flake and a resin composition of a thermoplastic resin, the present inventors conform to ASTM D-1504. The measured heat shrinkage stress of the glitter sheet may be 0.1 to 3.0 Mpa. However, in order to prevent the occurrence of peeling caused by stretching the glitter sheet, the glitter sheet is preferably used. Was found to have a heat shrinkage stress of 0.1 to 1 MPa. That is, by setting the heat shrinkage stress of the brilliant sheet to 0.1 Mpa or more, it has good impact resistance, especially low-temperature impact resistance, and by setting it to 1 Mpa or less, it can be used for thermoforming such as vacuum forming or pressure forming. The generated shrinkage due to the orientation return of the sheet can be suppressed, and defects such as uneven thickness which are likely to occur during heating can be prevented. Further, from the viewpoint of better mold reproducibility, the heat shrinkage stress is preferably in the range of 0.2 to 0.7 Mpa, more preferably 0.2 to 0.5 Mpa.
[0019]
Here, the heat shrinkage stress referred to in the present invention is measured in accordance with ASTM D-1504, and is a force that is shown when the stretched sheet is heated to restore the state before stretching when the stretched sheet is heated. Yes, it is obtained as a value obtained by dividing the maximum stress by the cross-sectional area of the sheet, and serves as an index indicating the degree of molecular orientation of the stretched sheet.
[0020]
Glass flakes generated by setting the heat shrinkage stress of a glittering sheet having a glittering layer made of a resin composition of a glittering glass flake and a thermoplastic resin within a range of 0.1 to 1 MPa, and stretching the glittering sheet. In order to prevent peeling at the interface with the glittering sheet, the glittering sheet is stretched at a stretching temperature of 110 to 140 ° C. and a longitudinal stretching direction (longitudinal direction, extrusion direction or machine direction) and a transverse stretching direction (a direction perpendicular to the longitudinal stretching direction). ), Preferably at a stretching ratio of 1.1 to 2.0 times, more preferably 1.1 to 1.6 times, and still more preferably 1.2 to 1.5 times. When the stretching ratio is less than 1.1 times, a heat shrinkage stress of 0.1 MPa at which sufficient sheet properties are exhibited cannot be obtained, and when the stretching ratio is greater than 2.0 times, interface peeling of glittering glass flakes occurs. And a good metallic luster cannot be obtained.
The stretching method may be sequential stretching or simultaneous biaxial stretching. Further, the stretching in the longitudinal stretching direction and the transverse stretching direction need not necessarily be performed in both directions at the same stretching ratio, and may be 1.1 to 2.0 times each.
[0021]
In the case of sequential biaxial stretching, it is general to first stretch in the longitudinal stretching direction and then stretch in the transverse stretching direction. Specifically, a method of combining stretching in the longitudinal stretching direction using a speed difference between rolls and stretching in the transverse stretching direction using a tenter is often used. For example, when a glitter sheet mainly using an acrylic resin for the glitter layer or the coloring layer is stretched in the longitudinal stretching direction, a temperature range of 110 to 135 ° C. is preferable, and the stretching is performed in the transverse stretching direction by a tenter method. The film may be stretched 1.1 to 2.0 times under a temperature condition of about 120 to 140 ° C.
[0022]
A coloring agent may be added to the glittering layer to such an extent that the metallic luster is not impaired. The amount of the coloring agent varies depending on the type of the coloring agent and the desired color tone, but in order to maintain the impact strength, 20 parts by mass relative to 100 parts by mass of the thermoplastic resin in the resin composition constituting the glittering layer. Parts by weight or less, more preferably 10 parts by weight or less. Even when a coloring agent is contained, the coloring layer or the base material layer provided on the back of the glittering layer, which will be described later, can be seen from the glittering layer surface, and has a total light transmittance of a level at which those colors can be confirmed. It is preferable that the glittering layer has a total light transmittance of 20% or more, since it can impart a subtle change in color to the three-dimensional effect (depth) and glittering properties, and can achieve excellent design. It is more preferable that the total light transmittance is 40% or more, since a good three-dimensional effect can be obtained with the conductive layer and the colored layer or the base material layer.
[0023]
The colorant to be used is not particularly limited, and common inorganic pigments, organic pigments, dyes, and the like used for coloring general thermoplastic resins can be used according to the intended design. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, composite oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; Pigment, phthalocyanine pigment, quinacridone pigment, dioxazine pigment, anthraquinone pigment, isoindolinone pigment, isoindoline pigment, perylene pigment, perinone pigment, quinophthalone pigment, thioindigo pigment and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments; It is preferable to use one or two dyes selected from the group of oil-soluble dyes.
[0024]
A first embodiment of the glittering sheet is a glittering sheet including the glittering layer. Furthermore, in addition to the glitter layer, the glitter sheet of the present invention may be configured to include a coloring layer, a base material layer, and a clear layer. The sheet will have even better properties.
[0025]
In a second embodiment of the glittering sheet, a coloring layer composed of a resin composition containing a coloring agent and a thermoplastic resin is provided on the back surface of the glittering layer, and the coloring layer is formed from the surface side of the glittering layer. This is a glitter sheet that allows at least a part of the coloring layer to be seen through.
The resin component of the resin composition constituting the colored layer is not particularly limited, but preferably has transparency and weather resistance and mechanical strength in a range that does not impair the coloring effect of the contained colorant. It is appropriately selected according to the intended layer structure of the glittering sheet.
For example, in the case of a glitter sheet used for forming a glitter layer of an injection-molded article having a glitter layer, a base material layer, which will be described below, is provided below the coloring layer in order to prevent the glitter sheet from being broken by injection molding. In general, in this case, the thermoplastic resin constituting the colored layer is preferably a resin of the same type as the glittering layer in terms of increasing the adhesiveness with the glittering layer, and an acrylic resin is particularly preferable. preferable.
[0026]
However, it is also possible to manufacture an injection-molded article without providing a base material layer. In this case, the thermoplastic resin constituting the colored layer constitutes a base material layer described later and a main body of the injection-molded product. It is preferable to use the same resin as the thermoplastic resin to be used in order to improve the adhesion with the thermoplastic resin constituting the main body of the injection molded article.
[0027]
Examples of the acrylic resin include, in addition to the acrylic resin used for the glittering layer, a graft copolymer of acrylonitrile or methacrylic ester onto a rubbery polymer. Among them, a homopolymer of methyl methacrylate or acrylonitrile, or a copolymer containing these as a main component is particularly preferable because of its excellent weather resistance and ultraviolet shielding effect. Also, by containing a coloring agent, a rubber-reinforced polymethylmethacrylic acid polymer in which seed-polymerized multi-structure crosslinked acrylic rubber is dispersed to prevent the impact resistance from lowering and to improve the weather resistance It is preferable to use
[0028]
A rubber-reinforced polymethylmethacrylic acid polymer in which a seed-polymerized multi-structure crosslinked acrylic rubber is dispersed is, for example, a seed-polymerized multiplex polymer described in JP-B-55-27576 and JP-A-1-252563. It is a rubber-reinforced polymethylmethacrylic acid polymer in which a structurally crosslinked acrylic rubber is dispersed. More specifically, a resin composition in which a multi-layer acrylic polymer including a rubber elastic layer is dispersed in an acrylic resin, wherein the inner layer is a soft rubber composed of a copolymer of an alkyl acrylate and a polyfunctional monomer, It is preferable that the outer layer has a two-layer structure of a hard polymer containing methyl methacrylate as a main component and contains a rubber elastic layer in an amount of 20 to 60% by weight.
[0029]
The amount of the colorant used in the resin composition constituting the color layer varies depending on the type of the colorant and the thickness and color tone of the target sheet, but in order to express the target color and maintain the impact strength. The amount is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the thermoplastic resin in the resin composition constituting the colored layer. When the amount of the coloring agent is less than 0.1 part by mass, the color development is not sufficient, and when the amount of the coloring agent exceeds 20 parts by mass, the impact strength tends to decrease.
[0030]
The colorant is not particularly limited, and pigments and dyes used in the glitter layer can be used. In addition, when the same glittering glass flakes as the glittering layer are used, there is an effect that the resulting glittering properties have a sense of depth. In addition, the same additives as those used for the glitter layer can be used as additives for preventing blurring, additives for improving three-dimensional appearance, and additives for improving glitter.
[0031]
A third embodiment of the glitter sheet is a glitter sheet in which a base layer made of a thermoplastic resin is provided on the back surface of the glitter layer.
The base material layer is arranged in a mold so that the glittering sheet is in contact with the female mold so as to form a glittering surface layer portion of the injection-molded product in the integral molding by injection molding such as insert molding or direct molding, When the thermoplastic resin is injected into the back surface of the glittering sheet and integrally molded, the molding strength of the glittering sheet is increased to prevent the glittering sheet from being broken by the injection resin, and the back surface of the glittering surface layer portion. Is provided for the purpose of increasing the adhesion between the glittering surface layer portion and the main body by bonding the base material layer provided in the above and the thermoplastic resin constituting the main body of the injection molded article. Therefore, it is preferable that the base material layer is a resin of the same kind as the main body made of a thermoplastic resin, or a resin having good adhesion to the thermoplastic resin.
[0032]
The thermoplastic resin constituting the main body of the injection-molded article preferably has excellent impact strength and thermoformability. For example, rubber-containing thermoplastic resins such as ABS, AAS and AES; acrylonitrile-styrene copolymer Resins such as (AS): a polymer alloy of the rubber-containing thermoplastic resin and polybutylene terephthalate, a polymer alloy of the rubber-containing thermoplastic resin and a polycarbonate resin, and a polymer alloy of the rubber-containing thermoplastic resin and a nylon resin. A polymer alloy with a rubber-containing thermoplastic resin such as a polymer alloy;
Thermoplastic elastomers (TPE) such as styrene-based elastomer (SBC), urethane-based elastomer (TPU), polyester-based elastomer (TPEE) and polyamide-based elastomer (TPAE) are exemplified.
[0033]
Among these, ABS, AAS, and a polymer alloy with a rubbery thermoplastic resin are preferable because they are particularly excellent in impact resistance and thermoformability. Among them, a polymer alloy with ABS and ABS is preferable. Are preferably a polymer alloy of ABS and polybutylene terephthalate resin, a polymer alloy of ABS and polycarbonate resin, and a polymer alloy of ABS and nylon resin. These may be used alone or in combination of two or more.
[0034]
The base layer may be non-colored, but it is preferable to include a colorant in the base layer, since the concealing property of the base color of the molded article is improved. Further, since the color of the base layer can be seen through from the surface side of the glittering layer, a three-dimensional appearance and a unique metallic color tone can be obtained, and the design property can be enhanced, which is preferable. The coloring agent used for the base layer can use a coloring agent that can be used for the coloring layer, the amount of the coloring agent added, in order to maintain moldability and impact strength, and to develop a sufficient color, It is 0.1 to 20 parts by mass relative to 100 parts by mass of the thermoplastic resin in the resin composition constituting the base material layer.
[0035]
In the fourth embodiment of the glittering sheet, a coloring layer composed of a resin composition containing a coloring agent and a thermoplastic resin is provided on the back surface of the glittering layer, and a thermoplastic resin is formed on the back surface of the coloring layer. A glitter sheet provided with a structured base layer and capable of seeing through at least a part of the coloring layer from the surface side of the glitter layer.
[0036]
For the coloring layer, the coloring agent and the thermoplastic resin used for the coloring layer described in the second embodiment are used, and for the base layer, the thermoplastic resin used for the base layer described in the third embodiment is used. Can be used respectively. By increasing the amount of the coloring agent added to the coloring layer so that the base layer can be seen through, the color of the base layer is added to the color of the coloring layer seen from the surface side of the glittering layer, increasing the sense of color depth In addition, a subtle metallic color tone can be developed from the difference in color between the colored layer and the base layer. For these, the amount and type of the colorant in the colored layer and the base material layer are appropriately selected according to the intended design.
[0037]
The fifth embodiment of the glitter sheet is a glitter sheet in which a clear layer made of a thermoplastic resin is provided on the surface of the glitter layer. By providing a clear layer made of a transparent resin on the glitter layer, the unevenness of the glitter sheet surface due to the shape of the glass flakes contained in the glitter layer can be reduced, and the surface smoothness of the glitter sheet is improved. As a result, the metallic gloss of the obtained glittering sheet increases.
[0038]
The transparent thermoplastic resin constituting the clear layer is preferably of the same type as the thermoplastic resin constituting the glittering layer because of its excellent adhesiveness. Among them, acrylic resin, polystyrene, AS resin, AES resin and the like are preferable. Transparent resins are preferred, and acrylic resins are particularly preferred. The thickness of the clear layer is preferably 5 μm or more because the metallic gloss is improved by being less affected by the glittering glass flakes, and is preferably 1000 μm or less to obtain sufficient thermoformability. Preferably it is 10 to 200 μm, more preferably 30 to 100 μm.
[0039]
A preferred glitter sheet having a clear layer is provided with a clear layer composed of a thermoplastic resin on the surface of the glitter layer, and a resin composition containing a colorant and a thermoplastic resin on the back surface of the glitter layer. A brilliant sheet provided with a structured colored layer, provided with a base layer made of a thermoplastic resin on the back surface of the colored layer, and capable of seeing through at least a part of the colored layer from the front side of the clear layer. It is.
[0040]
Here, for the coloring layer, the coloring agent and the thermoplastic resin used for the coloring layer described in the second embodiment are used, and for the base layer, the coloring agent is used for the base layer described in the third embodiment. Thermoplastic resins can each be used.
[0041]
To the glitter layer, the coloring layer, the base layer and the clear layer constituting the glitter sheet of the present invention, if necessary, conventional additives are added as long as their transparency, impact strength and moldability are not impaired. For example, plasticizers, lightfast additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, antiozonants, activators, antistatic agents, lubricants, antifriction agents, surface modifiers ( Leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants, and additives such as flow promoters and flow promoters may be added. These additives may be used alone or in combination of two or more.
[0042]
The glitter sheet of the present invention may be a sheet composed of one glitter layer, but may have a two-layer structure in which a colored layer is provided on the back surface of the glitter layer, or a clear layer provided on the surface of the glitter layer. A two-layer structure, a two-layer structure in which a base layer is provided on the back surface of a glitter layer, a three-layer structure in which a glitter layer, a coloring layer, and a base layer are laminated in this order, a clear layer, and a glitter layer , A three-layer structure in which a colored layer is laminated in this order, or a four-layer structure in which a clear layer, a glittering layer, a colored layer, and a base layer are laminated in this order. The glitter sheet of the present invention is such that a sheet having a glitter layer alone or a multilayer sheet including a glitter layer is stretched 1.1 to 2.0 times in each of the longitudinal stretching direction and the transverse stretching direction, and the heat shrinkage stress in both directions is reduced. Each of the glittering sheets has a brightness of 0.1 to 1 MPa.
[0043]
Among them, a glitter sheet having a two-layer structure in which a coloring layer is provided on the back surface of the glitter layer, a glitter sheet having a three-layer structure in which a glitter layer, a coloring layer, and a base layer are laminated in this order, A glitter sheet having a four-layer structure in which a clear layer, a glitter layer, a coloring layer, and a base layer are laminated in this order is preferably used in terms of design.
[0044]
As a method of laminating each layer, a wet lamination method, a dry lamination method, a solventless dry lamination method, a hot melt lamination method, an extrusion lamination method, a heat lamination method, a co-extrusion method, and the like are preferably used, and among them, a co-extrusion method or A lamination method by a thermal lamination method is preferred because the resulting sheet has a high adhesive strength and hardly causes delamination during stretching after lamination, and a multilayer sheet co-extrusion method is particularly preferred.
[0045]
Since the glittering sheet of the present invention needs to have both glittering properties, moldability and impact resistance, a four-layer sheet including a glittering layer alone, a clear layer, a glittering layer, a coloring layer, and a base layer is used. Even so, the thickness of the glitter sheet is preferably 30 to 1000 μm in total, and more preferably 50 to 500 μm. If the thickness of the glittering sheet exceeds 1000 μm and is too thick, the moldability is poor, and if it is less than 30 μm, mechanical properties such as impact resistance are inferior.
[0046]
The method for producing a glitter resin molded article of the present invention comprises a resin composition containing a glitter glass flake coated with at least one selected from the group consisting of a metal and a metal oxide, and a thermoplastic resin. A brilliant sheet having a brilliant layer and having heat shrinkage stresses of 0.1 to 1 MPa in the longitudinal stretching direction and the transverse stretching direction, respectively, is placed in a mold so as to be in contact with the female mold. And forming a glitter resin article by injection molding a thermoplastic resin on the back surface of the glitter sheet or the preformed body thereof.
[0047]
When performing insert injection molding, first, a glitter sheet is preformed to produce a preformed body. The preform is manufactured by thermoforming such as vacuum forming, hot plate press forming, or vacuum press forming. Among them, vacuum forming is simple and preferable. The surface temperature of the glitter sheet at the time of vacuum forming is not particularly limited, but a loss coefficient of a dynamic viscoelasticity measurement of a resin or a resin composition constituting the glitter sheet determined by a JIS K7244-1 method ( (tan δ) The temperature is preferably in a range of 5 ° C. to 20 ° C. higher than the glass transition temperature (Tg) represented by the maximum peak temperature.
Next, the obtained preform is placed in a mold so that its glittering layer is in contact with the female mold, and a thermoplastic resin is injection-molded on the back surface of the preform to be integrally molded.
[0048]
In the direct injection molding, the glitter sheet is arranged so that the glitter layer of the glitter sheet is in contact with the female mold of the injection molding machine without preforming the glitter sheet. At this time, the glitter film may use a single-piece insert film, or may arrange the glitter film wound up in a roll form intermittently. Next, similarly to the insert molding, a thermoplastic resin such as ABS or ABS-PBT alloy is melt-injected to be integrally molded. In addition, pre-molding may be performed by performing heat suction in a mold before performing injection molding.
[0049]
The present invention is a resin molded product in which a glittering surface layer portion and a main body portion made of a thermoplastic resin provided on the back surface of the glittering surface layer portion are integrally molded, wherein the glittering surface layer portion is made of metal and A glitter layer composed of a resin composition containing a glitter glass flake coated with at least one selected from the group consisting of metal oxides and a thermoplastic resin; and a glitter layer provided on the back surface of the glitter layer. A glitter layer comprising a resin composition containing a coloring agent and a thermoplastic resin, wherein at least a part of the colored layer can be seen through from the surface side of the glitter layer; Provide resin molded products.
[0050]
Various thermoplastic resins already described for each layer of the glitter sheet can be used for the glitter composition forming the glitter surface layer portion of the glitter resin molded article, the coloring layer and the resin composition constituting the base layer. Among them, the thermoplastic resin constituting the glitter layer is preferably a thermoplastic acrylic resin, and the thermoplastic resin constituting the colored layer and the thermoplastic resin constituting the main body are respectively a thermoplastic acrylic resin and a rubber. Alloy containing thermoplastic resin, rubber-containing thermoplastic resin and polybutylene terephthalate, polymer alloy containing rubber-containing thermoplastic resin and polycarbonate resin, polymer alloy containing rubber-containing thermoplastic resin and nylon resin, and heat It is at least one selected from the group consisting of plastic elastomers, so that the obtained glittering resin molded article has excellent impact resistance Preferably from and, more specifically, it is preferred rubber-containing thermoplastic resin of a polymer alloy is ABS.
[0051]
In the case where the glittering surface layer portion has a glittering layer, a coloring layer provided on the back surface of the glittering layer, and a base layer formed of a thermoplastic resin provided on the back surface of the coloring layer. The thermoplastic resin forming the glittering layer and the thermoplastic resin forming the coloring layer are each a thermoplastic acrylic resin, and the thermoplastic resin forming the base layer and the heat forming the main body portion are different from each other. Each of the plastic resins is a rubber-containing thermoplastic resin, a polymer alloy of a rubber-containing thermoplastic resin and polybutylene terephthalate, a polymer alloy of a rubber-containing thermoplastic resin and a polycarbonate resin, and a rubber-containing thermoplastic resin and nylon. The brilliant resin molded product is excellent in impact resistance when it is at least one selected from the group consisting of a polymer alloy with a resin and a thermoplastic elastomer. Preferable from the.
[0052]
The brilliant resin molded product provided by the present invention has an excellent metallic luster, and has a unique metallic color tone by having a brilliant layer and a see-through colored layer under the brilliant layer, and has excellent impact resistance. Therefore, it can be preferably used as an interior / exterior member of an automobile, a home electric appliance and the like.
[0053]
【Example】
Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto. In addition, the physical property evaluation in an Example and a comparative example was performed by the following measuring method or test method. In the examples, “parts” and “%” are based on mass.
[0054]
(1) Method for measuring heat shrinkage stress of glittering sheet
The glitter sheet was indirectly heated by mounting it between two hot plates heated to 200 ° C. (interval between the hot plates: 5 mm) in accordance with ASTM D-1504, and the shrinkage stress was measured.
[0055]
(2) Method for measuring total light transmittance of glittering sheet
Based on JIS K-7105, the total light transmittance of the glittering sheet was measured. In the case of a multilayer sheet, only the glitter layer was prepared and measured in advance.
[0056]
(3) Evaluation of molding state of vacuum molded product
The molding state of the bottom and the corners of the vacuum molded article prepared using the glitter sheet was evaluated according to the following evaluation criteria.
：: No abnormality.
Δ: No significant abnormality in appearance, but poor mold reproducibility such as corners.
X: The molded article has abnormal appearance such as uneven thickness.
[0057]
(4) Evaluation of molding condition of direct injection molded products
The molding state of the direct injection molded article prepared using the glitter sheet was evaluated according to the following evaluation criteria.
：: The glitter sheet is adhered well.
Δ: Some tears are observed in corners and the like.
×: The glittering sheet on the surface of the molded product was broken and a good molded product could not be obtained.
[0058]
(5) Design evaluation of vacuum molded and direct injection molded products
The appearance of the vacuum-formed product and the direct injection-molded product thus produced were visually evaluated according to the following evaluation criteria.
：: Good metallic luster without fogging. When the glittering surface layer portion includes a coloring layer containing a coloring agent or a base material layer, at least a part of the color of the coloring layer or the base material layer can be seen through the glittering surface layer.
Δ: Metallic luster, but cloudy or faint. Alternatively, although the metallic luster is sufficient, even when the glittering surface layer portion includes a coloring layer containing a coloring agent or a base material layer, the colors cannot be seen through the glittering surface layer.
×: Poor metallic luster.
[0059]
(6) Impact measurement of direct injection molded products
Using the created direct injection molded product, the presence or absence of cracks in the glittering sheet portion of each molded product at normal temperature (23 ° C) and low temperature (-25 ° C) was confirmed by a DuPont impact test according to JIS-K5400. Then, the 50% breaking strength was measured. The shooting type used had a radius of 1.6 mm. The evaluation criteria are as follows.
◎: 50% breaking strength of 0.5 J or more.
：: 50% breaking strength of less than 0.2 to less than 0.5 J.
C: 50% breaking strength of less than 0.1 to less than 0.2 J.
×: 50% breaking strength is less than 0.1 J.
[0060]
(Example 1)
For 100 parts by mass of polymethyl methacrylate (trade name “IRS704” 50% and “MD” 50% blend composition) manufactured by Mitsubishi Rayon Co., Ltd., Nippon Sheet Glass Co., Ltd. glass flake glittering material Metashine 5090PS02-M (average particle size) 90 μm, 5 μm in average thickness, 5 parts by mass of coated metal silver) were melt-kneaded and extruded from a T-die at 260 ° C. to produce a non-stretched raw sheet. The non-stretched raw sheet is mounted on a single-stretching machine and sequentially stretched 1.5 times in both the longitudinal stretching direction and the transverse stretching direction at 130 ° C., and a heat shrinkage stress of 0.5 MPa in the longitudinal stretching direction and the transverse stretching direction is applied. A glittering sheet was manufactured. Table 1 shows the evaluation results of the formed glitter sheet.
[0061]
(Layer structure)
Bright layer: 100 μm
[0062]
Using a small vacuum forming machine of FE38PH manufactured by Hermis Co., Ltd., the glittering sheet was heated indirectly from the glittering layer side of the glittering sheet, and after evacuation of the heater, the mold was raised from the opposite side to produce a vacuum molded product. The heating time was 20 seconds, the sheet temperature was 140 ° C. ± 3 ° C., the heater temperature was 370 ° C., the distance between the sheet and the heater was 130 mm, the mold temperature was 40 ± 3 ° C., and the vacuum / cooling time was 8 seconds. The used mold is designed to have a frontage of 113%, a bottom portion of 83 × 87mm, a depth of 42mm, a surface magnification of 170% at the center of the bottom surface, and a surface magnification of 260% at the corners. The area magnification here is expressed as 200% when the entire area is twice as large as the original area. Table 1 shows the evaluation results of the vacuum formed products.
[0063]
The PBT / ABS alloy heated to 250 ° C. was heated at a mold temperature of 80 ° C. after the obtained glitter sheet was adhered to the female mold of the injection mold so that the glitter layer of the glitter sheet was in contact with the female mold. A molten resin made of a resin was injected into a mold and integrally molded to prepare a direct injection molded product having a glittering surface layer portion. In addition, the injection molding machine is Sumitomo Nestal injection molding machine Promat 80/40 of Sumitomo Heavy Industries, Ltd. The mold is 65 mm × 40 mm × thickness 3 mm and 1.5 mm (thickness 3 mm) that can take a two-stage plate molded product. And a 1.5 mm two-stepped plate). Table 1 shows the evaluation results of the produced direct injection molded products.
[0064]
(Example 2)
For 100 parts by mass of polymethyl methacrylate (trade name “IRS704” 50% and “MD” 50% blend composition) manufactured by Mitsubishi Rayon Co., Ltd., Nissin Steel Co., Ltd. glass flake glittering material Crystal Star GF-1545 (average grain size) 2 parts by mass of a metal having a diameter of 40 μm, an average thickness of 1 μm, and a coating metal: Hastelloy were melt-kneaded and extruded from a T-die at 260 ° C. to produce a non-stretched raw sheet. The unstretched raw sheet was mounted on a single-stretching machine and stretched 2.0 times sequentially in both the longitudinal stretching direction and the transverse stretching direction at 130 ° C., and a heat shrinkage stress of 0.8 Mpa in the longitudinal stretching direction and the transverse stretching direction. A glitter sheet having the following layer constitution having the following was produced.
[0065]
(Layer structure)
Bright layer: 60 μm
[0066]
Using the obtained glittering sheet, a vacuum molded product was produced under the same conditions as in Example 1. Also, a PBT / ABS alloy resin was used as the injection molding resin in the same manner as in Example 1 to produce a direct injection molded product under the same conditions as in Example 1. Table 1 shows the evaluation results of the formed glitter sheet, vacuum molded product and direct injection molded product.
[0067]
(Example 3)
For 100 parts by mass of polymethyl methacrylate (trade name of “IRS704” 50% and “MD” 50%) manufactured by Mitsubishi Rayon Co., Ltd., a glass flake-based glittering material Crystal Star GF1345 (Nissin Steel Co., Ltd.) (average particle size: 45 μm) , An average thickness of 4 µm, and 1 part by mass of a coating metal (silver-tin alloy) were kneaded and dispersed to prepare a glittering resin composition for a glittering layer.
A pigment composed of 4 parts by mass of a diketropyrrole-based red, 0.5 parts by mass of calcined titanium yellow, and 0.5 parts by mass of titanium oxide, and 100 parts by mass of polymethyl methacrylate (trade name “HT03Y” manufactured by Sumitomo Chemical Co., Ltd.), and acrylic -A colored resin composition for a colored layer was prepared by kneading and dispersing 9 parts by mass of a mixture of a dispersant consisting of 4 parts by mass of a styrene copolymer.
[0068]
Using a hot press device, the glitter resin composition and the colored resin composition thus prepared were each press-molded under the conditions of a temperature of 200 ° C. and a pressure of 20 MPa, and then the two sheets obtained using the same hot press device. The press sheet was subjected to heat lamination at 140 ° C. and 2 MPa to obtain a two-layer raw sheet. The obtained two-layer raw sheet was mounted on a single-stretching machine and stretched at a temperature of 130 ° C. successively 1.5 times in the longitudinal stretching direction and the transverse stretching direction. A glitter sheet having a heat shrinkage stress of 5 Mpa and 0.5 Mpa in the transverse stretching direction was produced.
[0069]
(Layer structure)
Bright layer: 100 μm
Colored layer: 100 μm
[0070]
Using the obtained glittering sheet, a vacuum molded product was produced under the same conditions as in Example 1. Also, a PBT / ABS alloy resin was used as the injection molding resin in the same manner as in Example 1 to produce a direct injection molded product under the same conditions as in Example 1. Table 1 shows the evaluation results of the formed glitter sheet, vacuum molded product and direct injection molded product.
[0071]
(Example 4)
To 100 parts by mass of polymethyl methacrylate manufactured by Mitsubishi Rayon Co., Ltd. (a blend composition of 50% of “IRS704” and 50% of “MD”), Metashine 2040PS-M, a glass flake-based glittering material manufactured by Nippon Sheet Glass (average particle diameter 35 μm) A glossy resin composition for a glittering layer was prepared by kneading and dispersing 3 parts by mass of an average thickness of 1 μm and coated metal silver) and 1 part by mass of phthalocyanine blue as a coloring agent.
A colored resin composition for a colored layer was prepared by kneading and dispersing 4 parts by mass of phthalocyanine blue and 0.1 part by mass of carbon black with respect to 100 parts by mass of polymethyl methacrylate (trade name “HT03Y”) manufactured by Sumitomo Chemical Co., Ltd.
[0072]
Using a hot press device, the glitter resin composition and the colored resin composition thus prepared were each press-molded under the conditions of a temperature of 200 ° C. and a pressure of 20 MPa, and then the two sheets obtained using the same hot press device. The press sheet was heat-laminated under the conditions of 140 ° C. and 2 Mpa to obtain an original sheet having a two-layer structure. The obtained two-layer raw sheet was mounted on a single-stretching machine and stretched at a temperature of 130 ° C. successively 1.5 times in the longitudinal stretching direction and the transverse stretching direction. A glitter sheet having a heat shrinkage stress of 5 Mpa and 0.5 Mpa in the transverse stretching direction was produced.
[0073]
(Layer structure)
Bright layer: 200 μm
Colored layer: 200 μm
[0074]
Using the obtained glittering sheet, a vacuum molded product was produced under the same conditions as in Example 1. Also, a PBT / ABS alloy resin was used as the injection molding resin in the same manner as in Example 1 to produce a direct injection molded product under the same conditions as in Example 1. Table 1 shows the evaluation results of the formed glitter sheet, vacuum molded product and direct injection molded product.
[0075]
(Example 5)
100 parts by mass of polymethyl methacrylate (trade name “IRS704” and 50% “MD”) manufactured by Mitsubishi Rayon Co., Ltd. and 100% by mass of Nippon Sheet Glass Co., Ltd. A glittering resin composition for a glittering layer was prepared by kneading and dispersing 2 parts by mass of 25 μm, average thickness of 1.3 μm, and coated silver metal.
A pigment composed of 4 parts by mass of a diketropyrrole-based red, 0.5 parts by mass of calcined titanium yellow, and 0.5 parts by mass of titanium oxide, and 100 parts by mass of polymethyl methacrylate (trade name “HT03Y” manufactured by Sumitomo Chemical Co., Ltd.), and acrylic -A colored resin composition for a colored layer was prepared by kneading and dispersing 9 parts by mass of a mixture of a dispersant consisting of 4 parts by mass of a styrene copolymer.
[0076]
A pigment comprising 1 part by mass of a diketropyrrole-based red, 1 part by mass of calcined titanium yellow and 1 part by mass of titanium oxide, and 100 parts by mass of ABS resin (trade name “MTH2” manufactured by A & L Japan Co., Ltd.) and aluminum stearate 0.1 part by mass. A colored resin composition for a base material layer was prepared by kneading and dispersing 3.1 parts by mass of a dispersant mixture consisting of 1 part by mass.
The prepared three types of resin compositions were extruded at 260 ° C. using three extruders, and laminated in three layers by a feed block to produce a non-stretched raw sheet from a T-die. The prepared non-stretched raw sheet is stretched 1.2 times in the longitudinal stretching direction at 140 ° C. by a stretching roll device, and then stretched 1.2 times in the transverse stretching direction by a tent of 145 ° C. and wound up. A glitter sheet having a three-layer configuration and having a heat shrinkage stress of 0.4 Mpa in the longitudinal stretching direction and 0.2 Mpa in the transverse stretching direction was produced.
[0077]
(Layer structure)
Bright layer: 100 μm
Colored layer: 100 μm
Base layer: 300 μm
[0078]
Using an optical microscope (manufactured by OMRON Corporation, 3D digital fine scope VC1000, magnification: 1000 times), the glitter layer of the glitter sheet manufactured was measured, and it was found that the glitter material was well dispersed in the resin. confirmed. In addition, it was confirmed that the periphery of the glittering material was completely filled with the resin, and good metallic luster was exhibited because there were no voids.
[0079]
Using the obtained glittering sheet, a vacuum molded product was produced under the same conditions as in Example 1. Also, a PBT / ABS alloy resin was used as the injection molding resin in the same manner as in Example 1 to produce a direct injection molded product under the same conditions as in Example 1. Table 2 shows the evaluation results of the formed glitter sheet, vacuum molded product and direct injection molded product.
[0080]
(Example 6)
100 parts by mass of polymethyl methacrylate (trade name of "IRS704" 50% and "MD" 50% blend) manufactured by Mitsubishi Rayon Co., Ltd. A glittering resin composition for a glittering layer was prepared by kneading and dispersing 2 parts by mass of Metashine 2025PS-M (average particle size: 25 μm, average thickness: 1.3 μm, coated metal silver).
A pigment comprising 1 part by mass of a diketropyrrole-based red, 1 part by mass of calcined titanium yellow and 1 part by mass of titanium oxide, and 100 parts by mass of ABS resin (trade name "MTH2" manufactured by A & L Japan Co., Ltd.), and aluminum stearate 0.1 A colored resin composition for a colored layer was prepared by kneading and dispersing 3.1 parts by mass of a mixture of a dispersant consisting of parts by mass.
[0081]
As the prepared glittering resin composition for the glittering layer, the coloring resin composition for the coloring layer, and the resin composition for the clear layer, polymethyl methacrylate (trade name “IRS704” 50% and “MD”) manufactured by Mitsubishi Rayon Co., Ltd. "50% blend composition), extruding the three types of resin compositions at 260 ° C. using three extruders, and laminating them into three types of three layers of a clear layer / brilliant layer / colored layer by a feed block. A non-stretched raw sheet was produced with a T die. The produced non-stretched raw sheet is stretched 1.5 times in the longitudinal stretching direction at 140 ° C. by a stretching roll device, and then stretched 2.0 times in the transverse stretching direction by a tenter at 130 ° C. and wound up. A glitter sheet having a three-layer configuration and having a heat shrinkage stress of 0.3 Mpa in the longitudinal stretching direction and 0.5 Mpa in the transverse stretching direction was produced.
[0082]
(Layer structure)
Clear layer: 100 μm
Bright layer: 100 μm
Colored layer: 300 μm
[0083]
Using the obtained glittering sheet, a vacuum molded product was produced under the same conditions as in Example 1. Also, a PBT / ABS alloy resin was used as the injection molding resin in the same manner as in Example 1 to produce a direct injection molded product under the same conditions as in Example 1. Table 2 shows the evaluation results of the formed glitter sheet, vacuum molded product and direct injection molded product.
[0084]
As is clear from Tables 1 and 2, the glittering sheets, vacuum molded products and injection molded products prepared in Examples 1 to 6 all exhibited excellent metallic luster, moldability and impact resistance. In Tables 1 and 2, MD indicates the longitudinal stretching direction, and TD indicates the transverse stretching direction.
[0085]
(Example 7)
The stretched sheet obtained in Example 5 was subjected to vacuum forming under the same conditions as in Example 1 using a female mold having a length, width, and depth of 90 × 100 × 2.5 mm. The obtained molded product was cut off at the cut end to obtain a preformed product for insert injection molding. Next, the preformed product was inserted into an injection mold capable of obtaining a molded product having a length, width, and height of 90 × 100 × 2.5 mm, and insert injection molding was performed. The injection molding was performed under the same conditions using the PBT / ABS alloy resin used in the direct injection molding as the injection molding resin. As a result, as in the case of the direct injection molding of Example 5, an insert molded product having a good appearance was obtained.
[0086]
(Comparative Example 1)
The same resin composition used in Example 2 was extruded by the same method to produce a glitter sheet having a thickness of 60 μm. Evaluation was performed as an unoriented sheet without stretching. As a result, the sheet strength during molding heating was insufficient, the direct injection moldability was extremely poor, and the low-temperature impact resistance was also poor. Table 3 shows the evaluation results.
[0087]
(Comparative Example 2)
A non-stretched raw sheet having the same structure as in Example 5 was extruded to produce a glittering sheet having a thickness of 500 μm. Evaluation was performed as an unoriented sheet without stretching. As a result, direct injection moldability was poor due to insufficient strength of the sheet at the time of molding, and low-temperature impact resistance was also poor.
[0088]
(Comparative Example 3)
A non-stretched raw sheet having the same configuration as that made in Example 5 was extruded, and stretched 2.5 times in the longitudinal stretching direction using the same stretching apparatus as in Example 5 adjusted to 110 ° C. Then, the film is stretched and wound in a transverse stretching direction 2.5 times with a tenter at 115 ° C., and has the same three-layer structure as in Example 5, 1.4 MPa in the longitudinal stretching direction and 1.2 Mpa in the transverse stretching direction. A glittering sheet having a thickness of 500 μm and a heat shrinkage stress of
The obtained brilliant sheet did not show good metallic luster.
When the brilliant layer of the brilliant sheet was measured using an optical microscope (3D Digital Finescope VC1000, manufactured by OMRON Corporation, magnification: 1000 times), many white-like voids were generated around the brilliant material, It was presumed that light was diffusely reflected by these voids and metallic luster was reduced.
In addition, uneven thickness of the sheet occurred during heating during vacuum forming, and a vacuum-formed product having a uniform thickness could not be produced. Table 3 shows the evaluation results of the glittering sheets, vacuum molded products, and injection molded products prepared in Comparative Examples 1 to 4.
[0089]
[Table 1]

[0090]
[Table 2]

[0091]
[Table 3]

[0092]
【The invention's effect】
The glitter sheet of the present invention has a glitter layer composed of a resin composition containing a glitter glass flake coated with at least one selected from the group consisting of metals and metal oxides and a thermoplastic resin. Since it is a brilliant sheet that has been subjected to weak stretching with a heat shrinkage stress of 0.1 to 1 MPa each in the longitudinal stretching direction and the transverse stretching direction, it can be integrated by thermoforming or injection molding while maintaining excellent metallic luster. Can be molded.
A glitter sheet having a glitter layer provided on a colored layer exhibits a unique metallic color tone and designability by allowing at least one of the colored layer and the base layer to be seen through the glitter layer. Also, the glitter sheet provided with a clear layer on the glitter layer can reduce the influence of irregularities on the surface due to the shape of the glass flakes contained in the glitter layer by the clear layer, and can increase the surface smoothness. As a result, more excellent metallic luster is exhibited.
The glitter resin molded article of the present invention comprises a resin composition containing a glitter glass flake coated with at least one selected from the group consisting of metals and metal oxides as a glitter surface layer portion, and a thermoplastic resin. It has a glittering layer to be provided and a coloring layer provided on the back surface of the glittering layer, so that at least a part of the coloring layer can be seen through from the surface side of the glittering layer, excellent metallic luster, unique It has a metallic color and impact resistance, and is suitably used for interior and exterior members of automobiles, motorcycles, OA equipment, home electric appliances and the like.

Claims (15)

A glittering layer composed of a resin composition containing a glittering glass flake and a thermoplastic resin coated with at least one selected from the group consisting of metals and metal oxides; The glittering sheet, wherein heat shrinkage stress in each direction is 0.1 to 1 MPa. A colored layer composed of a resin composition containing a coloring agent and a thermoplastic resin is provided on a back surface of the glittering layer, and at least a part of the coloring layer can be seen through from a surface side of the glittering layer. Item 2. The glitter sheet according to item 1. The glitter sheet according to claim 1, wherein a base layer made of a thermoplastic resin is provided on a back surface of the glitter layer. The glitter sheet according to claim 1, wherein a clear layer made of a thermoplastic resin is provided on a surface of the glitter layer. A coloring layer made of a resin composition containing a coloring agent and a thermoplastic resin is provided on the back surface of the glittering layer, and a base material layer made of a thermoplastic resin is provided on the back surface of the coloring layer, The glitter sheet according to claim 1, wherein at least a part of the coloring layer can be seen through from the surface side of the glitter layer. A clear layer composed of a thermoplastic resin is provided on the surface of the glitter layer, and a colored layer composed of a resin composition containing a coloring agent and a thermoplastic resin is provided on the back surface of the glitter layer, The glittering sheet according to claim 1, wherein a base layer made of a thermoplastic resin is provided on a back surface of the coloring layer, and at least a part of the coloring layer can be seen through from a surface side of the clear layer. The glitter sheet according to claim 1, wherein the thermoplastic resin constituting the glitter layer is a thermoplastic acrylic resin. The glitter sheet according to claim 2, 5 or 6, wherein each of the thermoplastic resin forming the glitter layer and the thermoplastic resin forming the coloring layer is a thermoplastic acrylic resin. Each of the thermoplastic resin constituting the glitter layer and the thermoplastic resin constituting the colored layer is a thermoplastic acrylic resin, and the thermoplastic resin constituting the base layer is a rubber-containing thermoplastic resin, rubber. Alloys of rubber-containing thermoplastic resin and polybutylene terephthalate, polymer alloys of rubber-containing thermoplastic resin and polycarbonate resin, polymer alloys of rubber-containing thermoplastic resin and nylon resin, and thermoplastic elastomers The glitter sheet according to claim 5, which is at least one selected from the group. Each of the thermoplastic resin constituting the glitter layer, the thermoplastic resin constituting the colored layer, and the thermoplastic resin constituting the clear layer is a thermoplastic acrylic resin, and the thermoplastic resin constituting the base layer Resin is rubber-containing thermoplastic resin, polymer alloy of rubber-containing thermoplastic resin and polybutylene terephthalate, polymer alloy of rubber-containing thermoplastic resin and polycarbonate resin, polymer of rubber-containing thermoplastic resin and nylon resin The glitter sheet according to claim 6, wherein the glitter sheet is at least one selected from the group consisting of an alloy and a thermoplastic elastomer. A resin molded article in which a glittering surface layer portion and a main body portion made of a thermoplastic resin provided on the back surface of the glittering surface layer portion are integrally molded, wherein the glittering surface layer portion is made of metal and metal oxide. A glittering layer composed of a resin composition containing a glittering glass flake coated with at least one selected from the group consisting of a thermoplastic resin and a coloring agent provided on the back surface of the glittering layer; A glitter layer formed of a resin composition containing a thermoplastic resin, wherein at least a part of the glitter layer can be seen through from the surface side of the glitter layer. The thermoplastic resin forming the glitter layer is a thermoplastic acrylic resin, and the thermoplastic resin forming the coloring layer and the thermoplastic resin forming the main body are respectively a thermoplastic acrylic resin and a rubber-containing heat. From plastic resin, polymer alloy of rubber-containing thermoplastic resin and polybutylene terephthalate, polymer alloy of rubber-containing thermoplastic resin and polycarbonate resin, polymer alloy of rubber-containing thermoplastic resin and nylon resin, and thermoplastic elastomer The glitter resin molded product according to claim 11, which is at least one member selected from the group consisting of: The glitter surface layer portion includes the glitter layer, a colored layer provided on a back surface of the glitter layer, and a base layer formed of a thermoplastic resin provided on a back surface of the colored layer. 2. The glittering resin molded product according to item 1. The thermoplastic resin forming the glitter layer and the thermoplastic resin forming the coloring layer are thermoplastic acrylic resins, respectively, and the thermoplastic resin forming the base layer and the thermoplastic resin forming the body portion Are rubber-containing thermoplastic resin, a polymer alloy of rubber-containing thermoplastic resin and polybutylene terephthalate, a polymer alloy of rubber-containing thermoplastic resin and polycarbonate resin, a rubber-containing thermoplastic resin and nylon resin, The glitter resin molded article according to claim 13, which is at least one member selected from the group consisting of a polymer alloy and a thermoplastic elastomer. A glittering layer composed of a resin composition containing a glittering glass flake and a thermoplastic resin coated with at least one selected from the group consisting of metals and metal oxides; The glitter sheet having a heat shrinkage stress in each direction of 0.1 to 1 MPa is arranged in a mold so that the glitter layer of the glitter sheet or the preform thereof is in contact with the female mold, and the glitter sheet or the preforming thereof is formed. A method for producing a glittering resin molded product, comprising integrally molding a thermoplastic resin by injection molding on the back surface of a body.