Decorative laminated member and decorative molded article

Abstract

Provided are a decorative laminated member that imparts good design characteristics and excellent adhesion while suppressing the occurrence of warping, and a decorative molded article including the decorative laminated member. A decorative laminated member having a clear coating layer (A), a resin substrate layer (B), a design layer (C), an adhesive layer (D), and a heat-resistant film layer (E). The decorative laminated member is characterized in that the thermal shrinkage rate is 0% to 3.0% or less when the decorative laminated member is heated from 35°C to 105°C and then cooled from 105°C to 35°C.

Description

Decorative laminated materials and decorative molded products

[0001] The present invention relates to a decorative laminate member and a decorated molded article.

[0002] Conventionally, there is an insert molding method in which a decorative sheet is heated and preformed to fit the desired injection molding die, and then placed in the injection molding die so that molten resin is injected into the backing layer side. After that, injection molding is carried out to weld the molten resin to the backing layer, thereby integrating the decorative sheet and the molten resin, and after hardening, the insert molded product is removed from the injection molding die.

[0003] The decorative sheet not only provides a design to a molded body but also provides a surface protection function. Therefore, a certain level of surface hardness is required to prevent scratches. On the other hand, when a decorative sheet is attached to a molded body having a more complex shape, it is necessary to deform the sheet to fit the surface of the molded body to ensure close contact. For this reason, there has been a demand for the development of a decorative sheet that can achieve both surface protection function and high adhesion.

[0004] For example, Patent Document 1 discloses a topcoat-added decorative sheet having a topcoat layer on one side of the decorative sheet, wherein the topcoat layer has a surface hardness of pencil hardness B or higher at temperatures between −40 and 130° C. and an elongation rate of 150% or higher in a tensile test at 150° C. However, such a decorative sheet may be prone to warping (curling) due to inconsistencies in the heat shrinkage of the layers.

[0005] JP 2013-6346 A

[0006] In view of the above, the present invention aims to provide a decorative laminated member that has high designability and excellent adhesion and can suppress the occurrence of warping, and a decorative molded body that includes the decorative laminated member.

[0007] The present invention relates to a decorative laminate member having a clear coating layer (A), a resin substrate layer (B), a design layer (C), an adhesive layer (D), and a heat-resistant film layer (E), characterized in that the decorative laminate member has a thermal shrinkage rate of 0% or more and 3.0% or less when heated from 35°C to 105°C and then cooled from 105°C to 35°C. The decorative laminate member has a linear expansion coefficient of 0.8 x 10 －４ ~1.5 x 10 －４ The difference between the linear expansion coefficient upon cooling when the (clear coating layer (A) / resin substrate layer (B) / design layer (C)) laminate film is heated from 35° C. to 105° C. and then cooled from 105° C. to 35° C. and the linear expansion coefficient upon cooling when the heat-resistant film layer (E) is heated from 35° C. to 105° C. and then cooled from 105° C. to 35° C. is preferably 0.5×10 －４ When the heat-resistant film layer (E) is heated from 35° C. to 105° C. and then cooled from 105° C. to 35° C., the coefficient of linear expansion during cooling is preferably 0.8×10 －４ ~1.5 x 10 －４ (1 / °C) is preferred.

[0008] The resin substrate layer (B) is preferably made of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC, and has a thickness of 50 to 300 μm. The heat-resistant film layer (E) is preferably made of at least one of polypropylene resin, ABS resin, and PC-ABS resin.

[0009] The clear layer (A) is preferably formed from an after-cure radiation-curable clear coating layer-forming composition. The design layer (C) preferably contains an acrylic resin as a binder component and at least one of a luster material and a color pigment, and the luster material and color pigment are contained in an amount of 0.5 to 60 parts by mass in solids per 100 parts by mass of the total solids of the binder component, luster material, and color pigment. The present invention also relates to a decorated molded product obtained by pressing the above-mentioned decorative laminate member onto the surface of a molded product by insert molding.

[0010] The decorative laminate member of the present invention is suppressed from warping and is particularly suitable for insert molding.

[0011] 1 is a schematic diagram showing an example of a laminate structure of a decorative laminated member of the present invention. FIG. 2 is a diagram specifically showing a method for reading Tg from a chart in a method for measuring Tg in the present invention.

[0012] The present invention will be described in detail below. (Decorative Laminate Member) The decorative laminate member of the present invention has a laminate structure including essential components: a clear coating layer (A), a resin substrate layer (B), a design layer (C), an adhesive layer (D), and a heat-resistant film layer (E). Specifically, for example, it may have the laminate structure shown in FIG. 1. A film having such a configuration is adhered to a molded product by the heat-resistant film layer (E) to perform decoration. Furthermore, the decorative laminate member of the present invention may have a protective film layer (F) or the like, as necessary. These layers can be formed into various laminate forms as necessary.

[0013] The decorative laminate member of the present invention is characterized in that the thermal shrinkage rate when the decorative laminate member is heated from 35°C to 105°C and then cooled from 105°C to 35°C is 0% or more and 3.0% or less. The thermal shrinkage rate is more preferably 0% or more and 2.0% or less, and even more preferably 0% or more and 1.0% or less. When the decorative laminate member is heated from 35°C to 105°C and then cooled from 105°C to 35°C, the linear expansion coefficient during cooling is 0.8 x 10 －４ ~1.5 x 10 －４ (1 / °C). The linear expansion coefficient is preferably 0.9 x 10 －４~1.4 × 10 －４ In addition, the difference in linear expansion coefficient between the laminated film consisting of the clear coating layer (A), the resin substrate layer (B), and the design layer (C) when heated from 35°C to 105°C and then cooled from 105°C to 35°C and the heat-resistant film layer (E) when heated from 35°C to 105°C and then cooled from 105°C to 35°C is 0.5 × 10 －４ (1 / °C) or less. －４ (1 / °C) or less is more preferable. The present invention was completed by finding that by satisfying such requirements, warpage after preforming can be suppressed. Since the decorative laminate member of the present invention is one in which the above-mentioned warpage is suppressed, it can impart high adhesion to molded bodies having complex shapes. In addition, by using a heat-resistant film (E) with high smoothness, it is possible to suppress poor appearance such as citrus peel that occurs on the surface of the clear layer, and a decorated molded body with excellent design can be obtained.

[0014] The method for measuring the thermal shrinkage and linear expansion coefficient is described in detail below. First, a resin substrate layer (B) is coated with a composition for forming a clear coating layer, and after drying at 80 ° C. for 2 minutes, a protective film layer is attached without curing to form an uncured clear coating layer (A). Next, a coating composition for a design layer is coated on the side of the resin substrate layer (B) opposite the clear coating layer (A), and dried at 80 ° C. for 5 minutes to form a design layer (C). Next, a coating composition for an adhesive layer is coated on the design layer (C), and dried at 80 ° C. for 10 minutes to form an adhesive layer (D). Next, a heat-resistant film is laminated on the adhesive layer (D) to obtain a decorative laminate member. The obtained decorative laminate member is sampled in a size of 20 mm in length and 5 mm in width. The protective film layer (F) is peeled off to prepare a test piece, and the test piece is placed in the device so that the distance between the chucks is 10 mm and the tension between the chucks is 20 mN / min. Next, the test piece is heated and cooled under the conditions of temperature increase: 35°C to 105°C at 10°C / min, and temperature decrease: 105°C to 35°C at 5°C / min, and the distance between the chucks after the temperature has been decreased to 35°C is measured, and the thermal shrinkage is calculated using the following formula: Thermal shrinkage = |Distance between chucks after cooling - Distance between chucks before test (10 mm) | ÷ Distance between chucks before test × 100 Furthermore, when the test piece is heated and cooled under the above conditions, the linear expansion coefficient is calculated using the following formula from the distance between the chucks at 90°C when the temperature is decreased and the distance between the chucks at 35°C: Linear expansion coefficient = (Distance between chucks at 90°C - Distance between chucks at 35°C) ÷ Distance between chucks before test (10 mm) ÷ Temperature difference between 90°C and 35°C (55°C)

[0015] The linear expansion coefficient of the (clear coating layer (A) / resin substrate layer (B) / design layer (C)) laminate film can be measured in the same manner as above, except that a heat-resistant film is not laminated. Furthermore, the linear expansion coefficient of the heat-resistant film layer (E) can also be measured under similar conditions. The difference between the linear expansion coefficient of the obtained (clear coating layer (A) / resin substrate layer (B) / design layer (C)) laminate film and the linear expansion coefficient of the heat-resistant film layer (E) is defined as the linear expansion coefficient difference.

[0016] The difference in linear expansion coefficient can be adjusted by any method, for example, by adjusting the resin composition, production conditions, film thickness, etc. of each layer.

[0017] The heat-resistant film layer (E) has a linear expansion coefficient of 0.8×10 －４ ~1.5 x 10 －４ (1 / °C). If the linear expansion coefficient exceeds the upper limit, warping occurs in the preform film, and warping also occurs in the shape of the molded product after insert molding, so that the desired shape may not be obtained. The linear expansion coefficient is preferably 0.9 × 10 －４ ~1.4 × 10 －４ (1 / °C) is more preferable.

[0018] Each layer constituting the decorative laminate member will be explained below in order. (Clear Coating Layer (A)) The clear coating layer (A) is not particularly limited and may be a known clear coating layer used in decorative laminate substrates, but is preferably obtained from an after-cure type clear coating layer-forming composition described below.

[0019] Composition for forming a clear coating layer The clear coating layer contains a composition for forming a clear coating layer. The composition for forming a clear coating layer according to the present disclosure has unreacted (meth)acryloyl groups. Furthermore, a clear coating layer formed by applying the composition for forming a clear coating layer, for example, the clear coating layer of an unheated sample, has unreacted (meth)acryloyl groups. Furthermore, a fluence of 500 mJ / cm on the heated sample is ２ When exposed to active energy rays, the unreacted (meth)acryloyl groups in the clear coating layer are lost by 10 to 100% compared to the unreacted (meth)acryloyl groups in the clear coating layer of an unheated sample. A clear coating layer-forming composition having this relationship can set the crosslink density within a desired range, and the hard coat layer formed by curing the clear coating layer can have excellent physical properties. For example, a molded product can be obtained that has excellent abrasion resistance and chemical resistance, as well as high hardness. Such a clear coating layer and a composition for forming a clear coating layer can achieve, for example, the effects described below.

[0020] The clear coating layer-forming composition used for forming the clear coating layer according to the present disclosure is preferably a radiation-curable clear coating layer-forming composition, from the viewpoint of obtaining excellent hardness, etc. Among these, an active energy ray-curable clear coating layer-forming composition is more preferred.

[0021] Before being cured or semi-cured, the active energy ray-curable composition for forming a clear coating layer may be dried, for example, at a temperature of 80° C. to 120° C. Furthermore, the active energy ray-curable composition for forming a clear coating layer according to the present disclosure can be wound up with the protective film layer, the clear coating layer, and the resin substrate laminated in this order, and, for example, air entrapment between the protective film layer and the clear coating layer can be significantly reduced.

[0022] For example, the clear coating layer according to the present disclosure, which includes an active energy ray-curable composition for forming a clear coating layer, can significantly suppress defects due to external stress that may occur during the formation of a design layer, for example, during printing on a resin substrate. For example, defects such as dents and scratch marks can be suppressed, allowing for the production of molded products with excellent appearance.

[0023] In addition, the clear coating layer according to the present disclosure is preferable in that it can suppress curling, lifting, etc., due to differences in heat shrinkage between the protective film layer and the resin substrate. Furthermore, even if a complex shape is imparted to the decorative laminate member according to the present disclosure in a preforming process or the like, cracks, changes in appearance, bubbles, etc. do not occur.

[0024] (Resin Component) The active energy ray-curable clear coating layer-forming composition contains a resin component that forms the clear coating layer. Such a resin component preferably contains an active energy ray-curable component. The active energy ray-curable component is a monomer, oligomer, or polymer (also referred to as a resin) that can be crosslinked and cured by active energy rays (e.g., ultraviolet light). Specific examples of such active energy ray-curable components include monomers, oligomers, or polymers having at least one unsaturated double bond group, more specifically, (meth)acrylate monomers, (meth)acrylate oligomers, (meth)acrylate polymers, urethane (meth)acrylate monomers, urethane (meth)acrylate oligomers, urethane (meth)acrylate polymers, silicone (meth)acrylates, and modified monomers, oligomers, and polymers thereof, all of which have at least one unsaturated double bond group. These monomers, oligomers, and polymers may also be used in combination. Note that "(meth)acrylate" refers to acrylate and / or methacrylate. In one embodiment, the active energy ray-curable clear coating layer-forming composition contains an unsaturated double bond-containing acrylic resin (also referred to as an unsaturated double bond-containing acrylic polymer). In one embodiment, the clear coating layer-forming composition may contain a non-reactive acrylic resin. Furthermore, the clear coating layer-forming composition may contain an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin. The clear coating layer-forming composition may contain, for example, multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins.

[0025] For example, the active energy ray-curable component, e.g., the composition for forming a clear coating layer, contains an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight average molecular weight (Mw) of 5,000 to 100,000. In one embodiment, the unsaturated double bond-containing acrylic resin and / or the non-reactive acrylic resin may have a weight average molecular weight (Mw) of 5,000 or more and 100,000 or less, for example, a weight average molecular weight (Mw) of 6,000 or more and 95,000 or less. The weight average molecular weight (Mw) can be calculated by a known method.

[0026] In another embodiment, when the active energy ray curable component contains a plurality of polymers, one polymer may have a weight average molecular weight (Mw) of 5,000 or more and 100,000 or less, and another polymer may have a weight average molecular weight (Mw) of 10,000 or more and 80,000 or less. Furthermore, polymers having weight average molecular weights (Mw) of different ranges may be included. By using polymers having various weight average molecular weight ranges in combination, the clear coating layer can exhibit various properties such as high smoothness and high rigidity when uncured. In addition, the hard coating layer obtained by curing the clear coating layer can also have high smoothness and excellent hard coating performance, for example, high hardness, abrasion resistance and chemical resistance.

[0027] Although not intended to be limited to a particular theory, the inclusion of an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin can increase the rigidity of the uncured clear coating layer. Furthermore, the inclusion of at least one selected from the group consisting of polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates can maintain the crosslink density of the hard coating layer obtained by curing the clear coating layer, and the clear coating layer can have high viscosity at room temperature. Furthermore, the viscosity can be reduced upon heating, resulting in excellent moldability. As a result, even more complex shapes can be molded, and the occurrence of defective products during molding can be reduced. Furthermore, the resulting molded product can have better hard coating performance, such as higher hardness, abrasion resistance, chemical resistance, etc.

[0028] In one embodiment, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, and at least one selected from the group consisting of a polyfunctional (meth)acrylate and a polyfunctional urethane (meth)acrylate. For example, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin having a weight average molecular weight (Mw) of 5,000 to 100,000, and at least one selected from the group consisting of a polyfunctional (meth)acrylate having an acrylate equivalent of 50 to 500 and a polyfunctional urethane (meth)acrylate having an acrylate equivalent of 50 to 500.

[0029] In this specification, a non-reactive acrylic resin refers to an acrylic resin that does not react or shows almost no reactivity when irradiated with active energy rays, for example, an acrylic resin that does not react or shows almost no reactivity when irradiated with ultraviolet rays.

[0030] The acrylate equivalent of each of the polyfunctional (meth)acrylates and polyfunctional urethane (meth)acrylates is, for example, 50 or more and 500 or less, for example, 60 or more and 400 or less, and in another embodiment, 70 or more and 350 or less, and in yet another embodiment, 100 or more and 200 or less. By containing such a polyfunctional (meth)acrylate and / or polyfunctional urethane (meth)acrylate and the above-mentioned acrylic resin, air entrapment can be further suppressed, and a clear coating layer free of dust, scratches, etc. can be obtained. Furthermore, even if the shape is complex, molded products with excellent appearance can be obtained without defects such as cracks. In addition, molded products with excellent abrasion resistance and chemical resistance and high hardness can be obtained.

[0031] In one embodiment, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate, a fluororesin, and inorganic oxide fine particles. For example, the composition for forming a clear coating layer comprises an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, a polyfunctional silicon (meth)acrylate having a weight average molecular weight (Mw) of 700 to 100,000, a fluororesin, and inorganic oxide fine particles. While not intended to be limited to a particular theory, the inclusion of the polyfunctional silicon (meth)acrylate enables low surface tension, excellent leveling properties, and reduced tack. Meanwhile, the inclusion of the fluororesin can impart slip properties to the clear coating layer (coating). Furthermore, the inclusion of inorganic oxide fine particles can impart excellent abrasion resistance and reduce tack.

[0032] The weight average molecular weight (Mw) of the polyfunctional silicone (meth)acrylate is, for example, 700 or more and 100,000 or less, in one embodiment 800 or more and 90,000 or less, and in another embodiment 800 or more and 85,000 or less.

[0033] In one embodiment, the fluorine content of the fluororesin is 5% by weight or more and 80% by weight or less, for example, 5% by weight or more and 75% by weight or less.

[0034] For example, the composition for forming a clear coating layer contains, per 100 parts by mass of solids contained in the composition, more than 20 parts by mass and not more than 60 parts by mass of an unsaturated double bond-containing acrylic resin and / or a non-reactive acrylic resin, for example, 30 parts by mass or more and not more than 60 parts by mass, and in some embodiments, 35 parts by mass or more and not more than 60 parts by mass. When the composition for forming a clear coating layer contains multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins, it is preferable that the total amount of the multiple types of unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins is within the above range. Here, in the present disclosure, 100 parts by mass of solids contained in the composition means, for example, the total of 100 parts by mass of resin solids such as unsaturated double bond-containing acrylic resins and / or non-reactive acrylic resins, such as the (meth)acrylic resins, polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional silicone (meth)acrylates, fluororesins, and photopolymerization initiators, and, when inorganic oxide fine particles are included, the solids of the inorganic oxide fine particles.

[0035] In one embodiment, the composition for forming a clear coating film layer contains 5 parts by mass or more and 70 parts by mass or less, for example, 10 parts by mass or more and 70 parts by mass or less, of a polyfunctional (meth)acrylate and / or a polyfunctional urethane (meth)acrylate, relative to 100 parts by mass of the solid content contained in the composition, and in another embodiment, 13 parts by mass or more and 68 parts by mass or less.

[0036] In one embodiment, the composition for forming a clear coating layer contains 5 parts by mass or more and 50 parts by mass or less, for example, 10 parts by mass or more and 48 parts by mass or less, and in another embodiment, 15 parts by mass or more and 48 parts by mass or less, of polyfunctional silicon (meth)acrylate per 100 parts by mass of solids contained in the composition.

[0037] In one embodiment, the composition for forming a clear coating film layer contains 0.1 parts by mass or more and 10 parts by mass or less, for example, 1 part by mass or more and 8 parts by mass or less, of a fluororesin relative to 100 parts by mass of the solid content contained in the composition, and in another embodiment, 1.5 parts by mass or more and 7 parts by mass or less.

[0038] In one embodiment, the composition for forming a clear coating layer contains inorganic oxide fine particles in an amount of 1 part by mass to 55 parts by mass, for example, 10 parts by mass to 50 parts by mass, and in another embodiment, 12 parts by mass to 40 parts by mass, per 100 parts by mass of the solid content of the composition. By including inorganic oxide fine particles in the composition for forming a clear coating layer in such a range, rigidity can be imparted to the uncured coating film, resulting in, for example, a better coating film appearance. The appearance of the resulting molded product can be maintained well. Furthermore, the abrasion resistance of the cured coating film can be improved.

[0039] In one embodiment, the clear coating layer-forming composition in a state not irradiated with active energy rays is a composition in which the shape of the molecular weight distribution does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. For example, the coating composition contained in the clear coating layer of heated sample (1) for stretching test, which is a sample before irradiation with active energy rays, is a composition in which the shape of the molecular weight distribution does not change before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C. Here, "no change in the shape of the molecular weight distribution" means that, for the weight-average molecular weight peak, or for each molecular weight peak if there are multiple molecular weight peaks, the height shift and lateral shift of each molecular weight peak before and after heating for 30 to 60 seconds in an atmosphere of 150 to 190°C are both within a range of ±5%.

[0040] From the viewpoint that the composition for forming a clear coating layer according to the present disclosure can increase the crosslink density after curing, can increase the effect of improving surface hardness, and can increase the effect of improving transparency, it is preferred that the composition contains: a polyfunctional (meth)acrylate compound such as a polyfunctional (meth)acrylate monomer, a polyfunctional (meth)acrylate oligomer, or a polyfunctional (meth)acrylate polymer (in this specification, a polyfunctional (meth)acrylate compound may be abbreviated as "polyfunctional (meth)acrylate"); a polyfunctional urethane (meth)acrylate compound such as a polyfunctional urethane (meth)acrylate monomer, a polyfunctional urethane (meth)acrylate oligomer, or a polyfunctional urethane (meth)acrylate polymer (in this specification, a polyfunctional urethane (meth)acrylate compound may be abbreviated as "polyfunctional urethane (meth)acrylate"); It is preferable to include at least one selected from polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and polyfunctional silicon (meth)acrylate compounds such as polyfunctional silicon (meth)acrylate monomers, polyfunctional silicon (meth)acrylate oligomers, and polyfunctional silicon (meth)acrylate polymers (in this specification, polyfunctional silicon (meth)acrylate compounds may be abbreviated as "polyfunctional silicon (meth)acrylate");

[0041] Commercially available (meth)acrylate monomers or oligomers having one unsaturated double bond group may be used, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, acrylic acid, methacrylic acid, isostearyl (meth)acrylate, ethoxylated o-phenylphenol acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, N-methylol(meth)acrylamide, and N-hydroxy(meth)acrylamide.

[0042] The polyfunctional (meth)acrylate monomer or oligomer may be modified as necessary. However, in this specification, neither "polyfunctional urethane (meth)acrylate" nor "polyfunctional silicon (meth)acrylate" is included in the "polyfunctional (meth)acrylate."

[0043] Commercially available polyfunctional (meth)acrylate monomers or oligomers may be used. Examples of commercially available products include DPHA (manufactured by Daicel Allnex Corporation), PETRA (manufactured by Daicel Allnex Corporation: pentaerythritol triacrylate), PETIA (manufactured by Daicel Allnex Corporation), Aronix M-403 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta- and hexaacrylate), Aronix M-402 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta- and hexaacrylate), Aronix M-400 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta- and hexaacrylate), SR-399 (manufactured by Arkema: dipentaerythritol hydroxypentaacrylate), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and KAYARAD DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-404, M-405, M-406, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (all manufactured by Toagosei Co., Ltd.), KAYARD Examples of compounds that can be used include D-310, D-330, DPHA, and DPHA-2C (all manufactured by Nippon Kayaku Co., Ltd.), Nikalac MX-302 (manufactured by Sanwa Chemical Co., Ltd.), A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, and A-DPH (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0044] Examples of the monofunctional or polyfunctional (meth)acrylate polymer include high molecular weight compounds of the above-mentioned monofunctional or polyfunctional (meth)acrylate monomers or oligomers.

[0045] In this specification, the above-mentioned various polymers may be simply referred to as unsaturated double bond-containing acrylic polymers or unsaturated double bond-containing acrylic resins.

[0046] As the polyfunctional urethane (meth)acrylate monomer or oligomer, commercially available products may be used. Commercially available products include, for example, bifunctional urethane (meth)acrylates ("UX-2201", "UX-8101", and "UX-6101" manufactured by Nippon Kayaku Co., Ltd., "UF-8001" and "UF-8003" manufactured by Kyoeisha Chemical Co., Ltd., and "Ebecryl 244", "Ebecryl 284", "Ebecryl 2002", "Ebecryl 4835", "Ebecryl 4883", "Ebecryl 8807", and "Ebecryl 6700" manufactured by Daicel-Allnex Co., Ltd.), trifunctional urethane (meth)acrylates ("Ebecryl 254", "Ebecryl 264", and "Ebecryl 265" manufactured by Daicel-Allnex Co., Ltd.), and tetrafunctional urethane (meth)acrylates (Daicel "Ebecryl 8210" manufactured by Daicel Allnex Co., Ltd.), hexafunctional urethane (meth)acrylate ("Ebecryl 1290k", "Ebecryl 5129", "Ebecryl 220", "KRM8200", "Ebecryl 1290N" manufactured by Daicel Allnex Co., Ltd.), 9-functional urethane (meth)acrylate ("KRM7804" manufactured by Daicel Allnex Co., Ltd.), 10-functional urethane (meth)acrylate ("KRM8452", "KRM8509" manufactured by Daicel Allnex Co., Ltd.), 15-functional urethane (meth)acrylate (Daicel Allnex Co., Ltd.) Examples of resins that can be used include "KRM8655" manufactured by Allnex Co., Ltd., Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-904, Art Resin UN-901T, Art Resin UN-905, and Art Resin UN-952 (all manufactured by Negami Chemical Industrial Co., Ltd.), U-6HA, U-15HA, UA-100H, U-4HA, U-6LPA, UA-32P, U-324A, and U-4H (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0047] Monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers can also be prepared, for example, by reacting a polycarbonate diol, a (meth)acrylate compound containing a hydroxyl group and an unsaturated double bond group in the molecule, and a polyisocyanate.

[0048] Examples of the monofunctional or polyfunctional urethane (meth)acrylate polymer include high molecular weight compounds of the above-mentioned monofunctional or polyfunctional urethane (meth)acrylate monomers or oligomers.

[0049] The polyfunctional silicon (meth)acrylate monomer or oligomer is a compound having a silicone skeleton. For example, a compound having a silicone skeleton may have a fluorine atom-containing group, or a fluororesin may have a silicone skeleton. As the polyfunctional silicon (meth)acrylate monomer or oligomer, a commercially available product may be used. Examples of commercially available products include the following: Compounds having a methacryloyl group and an acryloyl group: BYK Corporation: BYK-UV3500, BYK-UV3570; Shin-Etsu Chemical Co., Ltd.: Shin-Etsu Silicone X-22-164, Shin-Etsu Silicone X-22-164AS, Shin-Etsu Silicone X-22-164A, Shin-Etsu Silicone X-22-164B, Shin-Etsu Silicone X-22-164C, Shin-Etsu Silicone X-22-164E, Shin-Etsu Silicone X-22-174DX, Shin-Etsu Silicone X-22-2426, Shin-Etsu Silicone X-22-2475, KER-4000-UV, KER-4700-UV, KER-4710-UV, KER-4800-UV, Examples of materials that include: FM-0711, FM-0721, FM-0725, TM-0701, FM-7711, FM-7721, and FM-7725 manufactured by JNC Corporation; TEGO (registered trademark) Rad 2010 and TEGO (registered trademark) Rad 2011 manufactured by Evonik Japan; materials having a fluorine atom-containing group containing a (meth)acryloyl group and a fluororesin having a silicone skeleton compound; Shiko UV-AF305 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.; ZX-212 and ZX-214-A manufactured by T&K TOKA; and KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.

[0050] The active energy ray-curable clear coating layer-forming composition may contain, for example, a fluorine-based resin in addition to the resins described above. When the composition contains a fluorine-based resin, the abrasion resistance of the molded product can be further improved. In the present disclosure, the fluorine-based resin refers to a fluorine-containing resin that does not contain a silicone skeleton compound. Examples include perfluorooctyl acrylate and acrylic-modified perfluoropolyether. The fluorine-containing resin may have a modified functional group, such as a methacryloyl group or an acryloyl group. The fluorine-based resin may be, for example, the following commercially available products. DIC: Megafac RS-72-K, Megafac RS-75, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-77; Daikin Industries: Optool DAC-HP; Solvay Solexis: FLUOROLINK MD700, FLUOROLINK AD1700; Neos: Ftergent 601ADH2, etc.

[0051] Furthermore, the composition for forming a clear coating layer does not develop tack in an uncured state, and the clear coating layer can be prevented from attracting dust. Furthermore, the occurrence of poor appearance of the clear coating layer when the protective film layer is peeled off can be prevented or significantly reduced.

[0052] In one embodiment, the composition for forming a clear coating layer contains inorganic oxide fine particles. The inorganic oxide fine particles may be inorganic oxide fine particles whose particle surfaces are modified with unsaturated double bonds. Examples of inorganic oxide fine particles include silica (SiO ２Examples of inorganic oxide particles include silica particles, alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (ATO) particles, and zinc oxide particles. Among these, silica particles and alumina particles are preferred from the standpoints of cost and paint stability, and those modified with functional groups are also preferred. The functional group is preferably a (meth)acryloyl group. The primary particle size of inorganic oxide fine particles, for example, is 5 nm to 100 nm from the standpoints of transparency and paint stability. The average particle size of the granular material in this specification is a value measured using image processing software from cross-sectional electron microscope images. For example, by incorporating inorganic oxide fine particles, volume shrinkage of an uncured coating film can be reduced. Furthermore, for example, by incorporating inorganic oxide fine particles, in addition to the above-mentioned effects, rigidity can be imparted to the coating film. Furthermore, by incorporating inorganic oxide fine particles, curling due to cure shrinkage can be suppressed in a cured coating film. For example, by incorporating inorganic oxide fine particles, abrasion resistance can be imparted in addition to the above-mentioned effects.

[0053] For example, commercially available inorganic oxide fine particles may be used. Examples of silica particles (colloidal silica) include IPA-ST, MEK-STM, IBK-ST, PGM-ST, XBA-ST, MEK-AC-2101, MEK-AC-2202, MEK-AC-4101M, and IBK-SD manufactured by Nissan Chemical Industries, Ltd.; PL-1-IPA, PL-1-TOL, PL-2-IPA, PL-2-MEK, and PL-3-TOL manufactured by Fuso Chemical Co., Ltd.; OSCAL series and ELECOM series manufactured by JGC Catalysts and Chemicals, Ltd.; and NANOBYK-3605 manufactured by BYK Japan K.K. Examples of alumina particles include AS-150I and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd., and NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610 manufactured by BYK Japan KK.

[0054] (Photopolymerization initiator) The composition for forming a clear coating film layer of the present invention preferably contains a photopolymerization initiator. The presence of the photopolymerization initiator allows the resin component to be successfully polymerized by active energy rays, for example, ultraviolet rays. Examples of the photopolymerization initiator include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, and oxime ester-based polymerization initiators. Examples of alkylphenone photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and the like. Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Examples of the titanocene photopolymerization initiator include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, etc. Examples of the oxime ester polymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.These photopolymerization initiators may be used alone or in combination of two or more.

[0055] Of the above photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2,2-dimethoxy-1,2-diphenylethan-1-one are more preferably used.

[0056] The amount of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, for example, 1 to 10 parts by mass, relative to 100 parts by mass of the solid content of the composition for forming a clear coating layer. The photopolymerization initiator may be used alone, or two or more types of photopolymerization initiators may be used in combination.

[0057] (Solvent) The composition for forming a clear coating layer may contain a solvent. The solvent is not particularly limited and can be appropriately selected taking into consideration the components contained in the composition, the type of substrate to be coated, the method of coating the composition, etc. Specific examples of solvents that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; and halogenated solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferably used.

[0058] Various additives can be added to the clear coating layer forming composition as needed. Examples of such additives include commonly used additives such as antistatic agents, plasticizers, surfactants, antioxidants, UV absorbers, light stabilizers, surface conditioners, and leveling agents. By including the above-mentioned additives in the clear coating layer forming composition, the durability of the decorative molded member and the decorative molded article can be further improved. As these additives, additives commonly used in the field of clear coating layer formation can be used.

[0059] The composition for forming the clear coating layer can be prepared by a method commonly used by those skilled in the art, for example, by mixing the above-mentioned components using a commonly used mixing device such as a paint shaker or a mixer.

[0060] (Resin Substrate Layer (B)) Examples of the resin substrate layer according to the present disclosure include highly transparent resin substrates such as polyester films such as polycarbonate films, polyethylene terephthalate, and polyethylene naphthalate; cellulose films such as diacetyl cellulose and triacetyl cellulose; and acrylic films such as polymethyl methacrylate (PMMA). Examples of the resin substrate layer include styrene films such as polystyrene and acrylonitrile-styrene copolymers; olefin films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; and amide films such as nylon and aromatic polyamides. Examples of the resin substrate layer include resin substrates such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, epoxy resins, and blends of the above polymers. Furthermore, the resin substrate layer may be a laminate of multiple resin substrates. For example, the resin substrate may be a laminated member of a film made of an acrylic resin and a film made of a polycarbonate resin, or a laminated member of a sheet. As the resin substrate, at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC is preferred from the viewpoint of excellent weather resistance and shape stability, and PMMA is particularly preferred.

[0061] The resin substrate layer can be appropriately selected from these resin substrates depending on the application from those having optically low birefringence, those having a retardation controlled to ¼ (λ / 4) or ½ (λ / 2) of the wavelength (e.g., 550 nm), or even those having no birefringence controlled at all.

[0062] The thickness of the resin substrate layer can be appropriately selected depending on the application of the decorative laminated member, the member processing method, etc. In general, from the viewpoint of workability such as strength and handleability, the thickness is 100 μm or more and 500 μm or less, particularly 200 μm or more and 500 μm or less, and more preferably 200 μm or more and 400 μm or less.

[0063] (Design Layer (C)) The laminate film for decorating three-dimensional molded products of the present invention preferably comprises at least one design layer (C) to impart design. Examples of such layers include a design layer (C-1) formed from a colored coating composition, a design layer (C-2) formed by printing, and a metallic design layer (C-3). The design layer (C) may consist of any one of the layers described above, or may consist of multiple layers. A unique appearance can be obtained by combining these layers. Furthermore, poor appearance due to twisting or the like is more pronounced when a coating layer with a glossy finish is present. However, in the decorative laminate member of the present invention, even if the design layer is a coating layer with a glossy finish, the occurrence of shock lines can be sufficiently suppressed. The design layers (C-1) to (C-3) are described below.

[0064] (Design Layer (C-1) Formed from a Colored Coating Composition) The colored coating composition that can be used in forming the design layer (C-1) is not particularly limited, but preferably contains an acrylic resin and at least one of a lustrous material and a colored pigment. In addition to the above components, the colored coating composition may contain other components such as an ultraviolet absorber (UVA), a light stabilizer (HALS), a binder resin or crosslinking agent, a pigment, a surface conditioner, an antifoaming agent, a conductive filler, and a solvent. The colored coating composition may be one that is cured by irradiation with electromagnetic rays, or may be thermoplastic or thermosetting.

[0065] (Acrylic Resin) The acrylic resin contained in the colored coating composition is not particularly limited, but preferably has a weight-average molecular weight Mw of 10,000 to 200,000, and more preferably 30,000 to 150,000. If the weight-average molecular weight Mw is less than 10,000, the flexibility of the design layer (C) decreases, and if the weight-average molecular weight Mw exceeds 200,000, it becomes difficult to produce the colored coating composition and apply it to a film.

[0066] The acrylic resin preferably has a Tg of −30° C. to 30° C. If the Tg is less than −30° C., problems such as reduced tackiness (blocking) of the coating film after coating and drying may occur, whereas if the Tg is greater than 30° C., problems such as poor molding due to increased coating film hardness and reduced low-temperature physical properties of the product may occur.

[0067] The binder component used in the design layer may contain, in addition to acrylic resin, thermoplastic resin such as cellulose resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, or styrene resin.

[0068] In this specification, Tg refers to a value measured using a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)) in the following steps: step 1: increasing the temperature from 20°C to 150°C at a temperature increase rate of 10°C / min; step 2: decreasing the temperature from 150°C to -50°C at a temperature decrease rate of 10°C / min; and step 3: increasing the temperature from -50°C to 150°C at a temperature increase rate of 10°C / min; and the value obtained from the chart during temperature increase in step 3. That is, the temperature indicated by the arrow in the chart shown in Figure 2 was taken as Tg.

[0069] (Luminous Material) The luminous material is not particularly limited, and is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments, and organic pigments. More specifically, examples thereof include metallic pigments using metallic luminous materials such as coated aluminum, aluminum flakes, copper, zinc, nickel, tin, aluminum oxide, and other metals or alloys; and mica pigments such as interference mica and white mica.

[0070] (Coloring Pigment) Examples of coloring pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. Examples of inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

[0071] The colored coating composition preferably contains 0.5 to 60 parts by mass of the lustrous material and the color pigment in terms of solid content per 100 parts by mass of the total solid content of the binder component, the lustrous material, and the color pigment.

[0072] (Other Components) Examples of other components contained in the colored coating composition, such as binder resins and crosslinkers, include modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, and blocked isocyanate compounds. The solvent contained in the colored coating composition may be one or a combination of two or more organic solvents typically used in coatings, such as esters, ethers, alcohols, amides, ketones, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. When using the above solvents, if volatile substances remain in the laminate film, they may volatilize during decoration of the substrate, causing pinholes and blisters. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminate film.

[0073] (Design Layer (C-2) Formed by Printing) The laminate film for decorating three-dimensional molded products of the present invention may have a design layer (C-2) formed by printing. The printing method is not particularly limited, and the layer may be formed by a known method such as inkjet printing, screen printing, offset printing, or flexographic printing. In particular, inkjet printing is preferred because it allows various printed layers to be formed inexpensively. Furthermore, printing may be performed using an energy ray-curable ink.

[0074] (Metallic Design Layer (C-3)) In order to obtain an excellent metallic appearance as if it were made of metal, the present invention forms a coating layer (C-3a) containing vapor-deposited aluminum or a vapor-deposited metal layer (C-3b) made of indium or tin. By forming a metallic design layer such as (C-3a) or (C-3b) above, not only can a good metallic appearance be obtained, but also decoration with a good metallic look can be performed without causing cracking or whitening due to stretching when decorating a three-dimensional molded product.

[0075] Such metallic design layers are coating layers (C-3a) containing vapor-deposited aluminum or vapor-deposited metal layers (C-3b) made of indium or tin, which will be described in detail below.

[0076] (Coating layer (C-3a) containing vapor-deposited aluminum) The first type of coating layer for forming the metallic design layer in the present invention is one formed from a paint containing a vapor-deposited aluminum pigment.

[0077] An example of such a coating layer (C-3a) containing a vapor-deposited aluminum pigment is one formed from a metallic base coating material containing 30 to 85% by weight of a vapor-deposited aluminum pigment based on the solid content of the coating material.

[0078] The vapor-deposited aluminum pigment is produced by shredding a vapor-deposited aluminum film into flakes. Such non-leafing vapor-deposited aluminum pigments can be produced by using a plastic film such as oriented polypropylene, crystalline polypropylene, or polyethylene terephthalate as a base film, applying a release agent thereto, and then vapor-depositing aluminum onto the release agent.

[0079] The vapor-deposited aluminum pigment is less particulate than ordinary aluminum pigments such as aluminum flakes, and can provide a design layer with a mirror-like appearance like a metal surface.

[0080] The vapor-deposited aluminum pigment is more preferably a non-leafing vapor-deposited aluminum pigment. The non-leafing vapor-deposited aluminum pigment preferably has a particle size of 3 to 20 μm and a thickness of 0.01 to 0.1 μm. By using a pigment having the above particle size, a new metallic design with less graininess can be achieved. The particle size is more preferably 5 to 15 μm. Note that the particle size in this specification is a value measured using a laser diffraction particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). Commercially available non-leafing vapor-deposited aluminum pigments that can be used in the present invention include Metasheen 11-0010, 41-0010, 71-0010, 91-0010, MS-750, MS-650 (manufactured by Ciba Specialty Co., Ltd.), and Silver Line P1000, P4100, Metalure L, Metalure A21010BG (manufactured by Ecart).

[0081] The leafing treatment is a treatment performed on the aluminum surface using a hydrophobic and / or oleophobic agent. The non-leafing vapor-deposited aluminum pigment used in the present invention is preferably a non-leafing vapor-deposited aluminum pigment that has not been subjected to such a leafing treatment. When leafing vapor-deposited aluminum is used, the adhesion between adjacent coating layers decreases, resulting in poor adhesion. Therefore, it is preferable to use non-leafing vapor-deposited aluminum in the present invention.

[0082] The vapor-deposited aluminum pigment is present in an amount of 30 to 85% by weight based on the total solids content of the coating layer (D-3a) containing the vapor-deposited aluminum. If the amount is less than 30% by weight, a bright coating film satisfying the dense metallic luster feeling cannot be obtained, and if the amount is more than 85% by weight, the physical properties of the coating film deteriorate. The content of the non-leafing vapor-deposited aluminum pigment is more preferably 40 to 80% by weight.

[0083] The coating layer (C-3a) containing vapor-deposited aluminum further contains a binder resin in addition to the non-leafing vapor-deposited aluminum pigment. Examples of the binder resin include, but are not limited to, vinyl chloride resin, acrylic resin, urethane resin, and polyester resin. Two or more of these may be mixed and used. Of these, vinyl chloride resin is particularly preferred.

[0084] The vinyl chloride resin may be commercially available. The vinyl chloride resin may be a homopolymer of vinyl chloride or a copolymer of vinyl chloride with other vinyl monomers copolymerizable with vinyl chloride. Specific examples of the copolymer include copolymers of vinyl chloride with vinyl acetate, maleic anhydride or its esters, vinyl ether, acrylic acid, and acrylic hydroxyl group-containing monomers.

[0085] The degree of polymerization of these vinyl chloride resins is usually 200 to 2000, preferably 300 to 1000. Commercially available vinyl chloride resins that are easily available include Solbin C, CN, A, TA2, TAO, TAOL, and M5 manufactured by Nissin Chemical Industry Co., Ltd.; Vinnol H11 / 59, E15 / 48A, LL4320, and E15 / 45M manufactured by Wacker; and VYHD, VAGD, VMCH, and VMCC manufactured by Dow UCAR. Two or more of these may also be used in combination.

[0086] The coating layer (C-3a) containing the vapor-deposited aluminum may contain an aluminum deflocculating agent. In this case, the aluminum deflocculating agent acts to suppress cohesive failure between the aluminum and the resin, which is preferable. Specific examples of the aluminum deflocculating agent that can be used include Dianal RE360 (manufactured by Mitsubishi Rayon Co., Ltd.).

[0087] The coating layer (C-3a) containing vapor-deposited aluminum may contain, in addition to the specific non-leafing vapor-deposited aluminum pigment, other luster pigments and / or color pigments. The other luster pigments and color pigments are not particularly limited, and examples thereof include the luster pigments and color pigments described above.

[0088] The metallic base paint for forming the coating film layer (C-3a) containing the vapor-deposited aluminum may contain, in addition to the above components, appropriate additives such as polyethylene wax, anti-settling agents, curing catalysts, ultraviolet absorbers, antioxidants, leveling agents, surface conditioners such as silicones and organic polymers, anti-sagging agents, thickeners, anti-foaming agents, crosslinkable polymer particles (microgels), etc. The metallic base paint may be in the form of a solvent-based paint, a water-based paint, etc.

[0089] The coating layer (C-3a) containing evaporated aluminum preferably has a thickness of 0.05 to 5 μm. If the thickness is outside this range, problems such as whitening and cracking are likely to occur, which is not preferred.

[0090] (Vapor-deposited metal layer (C-3b) made of indium or tin) First, the vapor-deposited metal layer will be described. Vapor deposition is a method of forming a thin film by heating and vaporizing a vapor deposition material in a vacuum container and attaching it to the surface of a substrate placed at a distance. In the present invention, the metals used for vapor deposition are tin and indium. For vapor deposition, 10 －３ ~10 －４ Since a vacuum of about 100 Pa is required, the container must first be evacuated. Therefore, deposition is a complete batch process, and continuous processing is not possible.

[0091] In addition, the deposition method for film generally involves (1) placing a film roll and a target metal in a chamber, (2) evacuating the chamber (10 －３ ~10 －４ (2) The target is heated and vapor is generated, which vaporizes the film surface. (3) When vapor deposition is complete, the chamber is opened to the atmosphere. Compared to direct vapor deposition on components, this process is more economically efficient because, despite being a batch process, one roll of film is processed continuously. Another advantage is that the thickness and quality of the vapor-deposited film can be easily controlled. However, the film itself cannot be used to create three-dimensional objects.

[0092] The vapor-deposited metal layer (C-3b) made of indium or tin in the present invention can be formed by a conventional vapor deposition method using these metals. The use of indium or tin allows for a metal layer with good elongation, so that cracking or whitening does not occur when forming into a three-dimensional shape, and there is no adverse effect on the appearance.

[0093] In the present invention, by using indium or tin as the vapor-deposited metal layer, there is an advantage that cracks and whitening are less likely to occur due to the effect of discontinuous vapor deposition.

[0094] When such a vapor-deposited metal layer is formed, its thickness is preferably 0.05 to 5 μm, which makes it possible to satisfactorily achieve the above-mentioned object.

[0095] (Adhesive Layer (D)) The adhesive layer (D) is composed of a thermoplastic elastomer (TPE), an acrylic resin (PMMA: Poly Methyl Methylate), a polycarbonate resin (PC: Polycarbonate), a polyester resin (PET: Polyethylene Terephthalate), a urethane resin or an epoxy resin, a tackifier, a softener, and the like. Thermoplastic elastomers include thermoplastic polystyrene (styrene-based elastomer) (TPS: Thermoplastic Polystyrene), thermoplastic polyurethane (TPU: Thermoplastic Polyurethane), thermoplastic polyolefin (TPO: Thermoplastic Olefin), thermoplastic polyester (TPE: Thermoplastic Polyester), thermoplastic polyamide (TPA: Thermoplastic Polyamide), polyvinyl chloride (PVC: Polyvinyl Chloride), polyvinyl butyral (PVB), etc. Among them, thermoplastic polystyrene is preferred from the viewpoints of heat resistance, weather resistance, and chemical resistance. The tackifier includes one or more resins selected from terpene resins, rosin resins, petroleum resins, coal resins, phenolic resins, xylene resins, etc. Examples of terpene resins that can be used include α-pinene terpene resins, β-pinene terpene resins, dipentene terpene resins, aromatic-modified terpene resins, terpene phenolic resins, and hydrogenated terpene resins. Examples of rosin resins include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, and modified rosin. Examples of petroleum resins that can be used include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymer (C5 / C9) petroleum resins, alicyclic (hydrogenated, dicyclopentadiene (DCPD)) petroleum resins, and styrene (styrene, substituted styrene) petroleum resins. Examples of coal resins that can be used include coumarone-indene resins.The softener contains one or more process oils selected from paraffinic process oil, naphthenic process oil, aromatic process oil, liquid polybutene, liquid polyisobutylene, etc. The thickness of the adhesive layer (D) is preferably in the range of 5 μm to 200 μm.

[0096] The adhesive layer (D) preferably contains a curing agent. When a curing agent is contained, it is preferable to use a polyisocyanate as the curing agent. The polyisocyanates that can be used are not particularly limited, and for example, those exemplified as those that can be used in forming the clear coating layer (A) can be used. When a curing agent is used, it is preferable to use an adhesive resin having a functional group reactive with the curing agent. Specifically, it is preferable to use one that has a hydroxyl group. In this case, the hydroxyl value is preferably 1 to 100 mgKOH / g. The lower limit is more preferably 2 mgKOH / g, and even more preferably 5 mgKOH / g. The upper limit is more preferably 80 mgKOH / g, and even more preferably 50 mgKOH / g. If the hydroxyl value is low, a sufficient crosslinked film cannot be obtained. If the hydroxyl value is high, the film after crosslinking may have poor stretchability, or the reaction with the isocyanate may be insufficient, leaving unreacted hydroxyl groups, which may result in poor performance such as water resistance.

[0097] The amount of polyisocyanate as a curing agent should be appropriately determined depending on the OH equivalent of the resin in the adhesive layer (D) and the NCO equivalent of the polyisocyanate, and is preferably mixed at a ratio of about 1:0.8 to 1:1.2, and is preferably 0.5 to 10 parts by weight relative to the total amount of the adhesive layer (D).

[0098] The pressure-sensitive adhesive layer (D) may contain components other than the adhesive resin, curing agent, and components for imparting design, as long as the components do not impair the object of the invention. Examples of such components include ultraviolet absorbers (UVA), light stabilizers (HALS), curing catalysts, antioxidants, surface conditioners, leveling agents, anti-sagging agents, thickeners, defoamers, conductive fillers, solvents, etc.

[0099] Furthermore, a solvent may be used to mix the components contained in the adhesive layer (D) or to adjust the viscosity. As the solvent, for example, one or a combination of two or more conventionally known organic solvents used in paints, such as esters, ethers, alcohols, amides, ketones, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, may be used. When using the above solvents, if volatile substances remain in the laminate film, the volatile substances may volatilize during decoration of the substrate, causing pinholes and blisters. Therefore, it is preferable to sufficiently reduce the amount of volatile substances contained in the laminate film.

[0100] (Heat-resistant film layer (E)) The heat-resistant film layer is intended to enhance adhesion to the molded article. The heat-resistant film layer is selected depending on the resin to be molded, but generally, polyolefin resins such as ABS resin and polypropylene resin, styrene resin, acrylic resin, vinyl chloride resin, polycarbonate resin, PC-ABS resin, etc. are preferred. Among these, it is preferable to include at least one of polypropylene resin, ABS resin, and PC-ABS resin.

[0101] The thickness of the heat-resistant film layer is preferably 100 to 500 μm. The thickness can be adjusted as appropriate, but it is preferable to adjust it so that it falls within the range of the linear expansion coefficient below.

[0102] (Protective Film Layer (F)) The decorative laminated member of the present invention may further have a protective film layer (F). The protective film layer (F) may be peelable or may not be peelable.

[0103] The resin film that can be used as the substrate of the protective film layer is not particularly limited. For example, it may be a polyolefin film such as a polyethylene film or a polypropylene film, a modified polyolefin film obtained by modifying these polyolefins and adding additional functions, a polyester film such as polyethylene terephthalate, polycarbonate, or polylactic acid, a polystyrene film, a polystyrene-based resin film such as an AS resin film or an ABS resin film, a nylon film, a polyamide film, a polyvinyl chloride film, a polyvinylidene chloride film, or a polymethylpentene film. Furthermore, if necessary, a film treated with an additive such as an antistatic agent or an ultraviolet inhibitor, or a film whose surface has been subjected to corona treatment or low-temperature plasma treatment, may be used.

[0104] In one embodiment, the resin film applicable to the substrate of the protective film layer is at least one film selected from polyethylene film, polystyrene film, modified polyolefin film, polymethylpentene film, unstretched polypropylene film (CPP film), and biaxially oriented polypropylene film (OPP film). In another embodiment, the resin film applicable to the substrate of the protective film layer is a polypropylene film, for example, an oriented polypropylene film (OPP film) or an unstretched polypropylene film (CPP film). The thickness of the protective film layer is not particularly limited, but preferably has a lower limit of 10 μm and an upper limit of 100 μm, and more preferably a lower limit of 20 μm and an upper limit of 80 μm.

[0105] Furthermore, an adhesive layer may be provided between the protective film layer and the clear coating layer, if necessary. By providing the adhesive layer in the protective film layer, the protective film layer can maintain its conformability and adhesion to the clear coating layer, and the uncured clear coating layer can be better protected from external factors (for example, scratches caused by the device, etc.), and air entrapment can be suppressed. Furthermore, even when the uncured clear coating layer and the protective film layer are wound up, such problems do not occur or can be significantly suppressed.

[0106] (Method for manufacturing decorative laminated member) Each layer other than the resin substrate layer (B) constituting the decorative laminated member of the present invention can be formed by preparing a coating composition in which the components constituting each layer are dissolved in a solvent, and applying and drying this on the resin substrate layer (B). In addition, when a protective film layer (E) is provided, a laminated structure can be obtained by laminating the protective film layer (E) on the laminated member thus formed.

[0107] The coating method for forming each of the above layers is not particularly limited, and may be, for example, spray coating using a sprayer, or coating using an applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. After the coating solution is applied by the above coating method, the coating solution can be formed by heating and drying to remove the solvent in the coating solution.

[0108] The heating and / or active energy ray irradiation for curing each of the above layers may be carried out sequentially for each layer after the layers are formed, or may be carried out after the entire laminate structure is formed. However, it is preferable to carry out the heating and / or energy ray irradiation after the preforming (shaping) step to cure the layer (after-cure).

[0109] As described above, the adhesive layer (D) may be bonded by a lamination method instead of a coating and drying method. That is, the adhesive layer (D) may be formed by preparing a film formed by the adhesive layer (D) and bonding it to a film by lamination.

[0110] (Method of Use) When decorating a molded product using the decorative laminate base material of the present invention, it may be carried out in the same manner as in the conventionally known methods, and is not particularly limited. That is, if necessary, the protective film layer (F) is peeled off from the decorative laminate member, and the heat-resistant film (E) is placed on the substrate surface, and the decorative laminate member is pressure-bonded to the substrate surface so as to be in close contact with the substrate surface. Then, electromagnetic wave irradiation or heating may be performed to harden each layer, thereby obtaining a coating film. Alternatively, the protective film layer (F) may be peeled off after pressure bonding and hardening. In addition, when the decorative laminate member is to be closely attached to the substrate surface, vacuum / pressure forming, vacuum forming, heating by injection molding, molding, etc. can be performed, and among these, it is particularly suitable for use in insert molding.

[0111] The present invention also relates to a decorated molded product comprising the above-described decorative laminate and a molded body. The method for producing the decorated molded product of the present invention is not particularly limited, but it is preferably obtained by the following insert molding method. The decorative laminate is preformed to fit a predetermined injection mold, and the shaped decorative laminate is placed in the injection mold. The injection mold is then closed, and molten resin is injected into the injection mold, and the cooled and solidified resin is integrated with the decorative laminate. Finally, after the molten resin has cooled and solidified, the injection mold is opened, and the insert molded product, whose surface is covered with the decorative laminate, is removed from the injection mold.

[0112] The molten resin is not particularly limited, and examples thereof include acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, polycarbonate resin, polystyrene resin, acrylic resin, polyester resin, polypropylene resin, and olefin-based elastomer resin.

[0113] Molded articles that can be suitably decorated with the decorative laminate member of the present invention are not particularly limited, and examples thereof include automobile exterior parts such as bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors; automobile interior parts such as instrument panels, center consoles, and door switch panels; housings for home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures; and bathroom vanities.

[0114] The present invention will be described below with reference to examples. In the examples, percentages used in the formulations are by weight unless otherwise specified. The present invention is not limited to the examples described below.

[0115] (Preparation of Pressure-Sensitive Adhesive Composition) 40 parts by mass of a styrene-based elastomer resin (thermoplastic polystyrene), 30 parts by mass of a tackifier, and 30 parts by mass of a softener were mixed in a container containing toluene to produce Pressure-Sensitive Adhesive Composition 1 with a solid content concentration of 35%.

[0116] (Preparation of clear coating layer-forming composition) In a vessel containing 185 parts of methyl isobutyl ketone, 15 parts by mass of KRM-8452 (manufactured by Daicel Allnex Corporation, multifunctional urethane acrylate 1) as an active energy ray-curable component, 40 parts by mass of Unidic V-6850 (manufactured by DIC Corporation, unsaturated double bond-containing acrylic resin), 40 parts by mass of Shikou UV-AF305 (manufactured by Mitsubishi Chemical Corporation, multifunctional urethane acrylate), and 5 parts by mass of a photopolymerization initiator (trade name: Omnirad 184, manufactured by IGM Resins) were mixed to produce a clear coating layer-forming composition 1 with a solids concentration of 35%.

[0117] (Preparation of coating composition for design layer) In a container containing methyl isobutyl ketone, 90 parts by mass of Coatax A228 (manufactured by Toray Fine Chemicals Co., Ltd.) as an acrylic resin, 9 parts by mass of Aluminum Paste 07-0674 (Toyo Aluminum K.K.) as a lustrous material, and Disparlon 6901-20X (manufactured by Kusumoto Chemicals Co., Ltd., anti-settling agent for aluminum pigments) as an additive were mixed to produce coating composition 1 for design layer with a solids concentration of 30%.

[0118] The resin substrates and heat-resistant films used are as follows: Resin substrate 1: Parapure HI-001 (Kuraray Co., Ltd., acrylic resin film, thickness 125 μm) Heat-resistant film 1: TP23030A (Okamoto Corporation, polypropylene resin film, thickness 400 μm) Heat-resistant film 2: PP film (Matai Co., Ltd., polypropylene resin film, thickness 450 μm) Heat-resistant film 3: 24UT097-1 (TOPPAN Corporation, polypropylene resin film, thickness 400 μm) Heat-resistant film 4: Parapure HI-001 (Kuraray Co., Ltd., acrylic resin film, thickness 125 μm)

[0119] <Preparation of Decorative Laminated Member 1> The clear coating layer-forming composition 1 was applied to the resin substrate layer 1 using an applicator so as to obtain a clear coating layer (A) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm, and dried at 80 ° C. for 2 minutes. A protective film was attached without UV curing to form a clear coating layer (A). Next, the design layer coating composition 1 was applied using an applicator to the opposite side of the clear coating layer (A) of the resin substrate layer 1 so as to obtain a design layer (C) having a dry film thickness of 20 μm, and then dried at 80 ° C. for 5 minutes to form the design layer (C). Next, the adhesive composition 1 was applied to the design layer (C) using an applicator so as to obtain an adhesive layer (D) having a dry film thickness of 25 μm, and dried at 80 ° C. for 10 minutes. Each heat-resistant film shown in Table 1 was laminated at room temperature to obtain a decorative laminated member.

[0120] (Measurement of Heat Shrinkage Ratio) The protective film of the prepared decorative laminate member was peeled off, and the heat shrinkage ratio of each test piece was measured according to the method described above. The results are shown in Table 1.

[0121] (Measurement of linear expansion coefficient) The linear expansion coefficient was measured according to the method described above for a test piece from which the protective film of the prepared decorative laminated member had been peeled off, and a test piece of a laminated film (clear coating layer (A) / resin substrate layer (B) / design layer (C)) prepared in the same manner except that the heat-resistant film was not laminated. The linear expansion coefficient was also measured for each of the heat-resistant films shown in Table 1. The results are shown in Table 1.

[0122] The resulting decorative laminate member was evaluated as follows. (Warpage after preforming) The resulting decorative laminate member was heated to 160°C in a vacuum forming machine and shaped into a plate measuring 100 mm length x 150 mm width x 2 mm height. After UV curing at 1000 mJ, the margins of the film other than the dimensions of 100 mm length x 150 mm width x 2 mm height were trimmed to produce a preformed film. The height of the highest part of the produced preformed film was measured and evaluated according to the following criteria. ◎: Height 3 mm or less ◯: Height 4 to 10 mm ×: Height 11 mm or more

[0123]

[0124] The decorative laminate member of the present invention can be particularly suitably used when decoration is carried out by insert molding.

[0125] (A) Clear coating layer (B) Resin substrate layer (C) Design layer (D) Adhesive layer (E) Heat-resistant film layer

Claims

1. A decorative laminated member having a clear coating layer (A), a resin base material layer (B), a design layer (C), an adhesive layer (D), and a heat-resistant film layer (E), wherein the heat shrinkage rate of the present decorative laminated member when heated from 35°C to 105°C and then cooled from 105°C to 35°C is 0% or more and 3.0% or less.

2. The coefficient of linear thermal expansion during cooling when the decorative laminated member is heated from 35°C to 105°C and then cooled from 105°C to 35°C is 0.8×10 －４ to 1.5×10 －４ ( / °C). The decorative laminated member according to claim 1.

3. When the (clear coating layer (A) / resin base material layer (B) / design layer (C)) laminated film is heated from 35°C to 105°C and then cooled from 105°C to 35°C, the coefficient of linear thermal expansion during cooling, and when the heat-resistant film layer (E) is heated from 35°C to 105°C and then cooled from 105°C to 35°C, the difference in the coefficient of linear thermal expansion during cooling is 0.5 × 10 －４ The decorative laminated member according to claim 1 or 2, wherein the difference is (1 / °C) or less.

4. When the heat-resistant film layer (E) is heated from 35°C to 105°C and then cooled from 105°C to 35°C, the linear expansion coefficient during cooling is 0.8 × 10 －４ to 1.5 × 10 －４ (1 / °C). The decorative laminated member according to claim 1 or 2.

5. The resin base material layer (B) is composed of at least one of polymethyl methacrylate (PMMA), polycarbonate (PC), and PMMA / PC, and has a thickness of 50 to 300 μm. The decorative laminated member according to claim 1 or 2.

6. The heat-resistant film layer (E) has a thickness of 100 to 500 μm. The decorative laminated member according to claim 1 or 2.

7. The heat-resistant film layer (E) contains at least one of polypropylene resin, ABS resin, and PC-ABS resin. The decorative laminated member according to claim 1 or 2.

8. The clear layer (A) is formed by an after-cure type radiation-curable clear coating layer-forming composition. The decorative laminated member according to claim 1 or 2.

9. The design layer (C) has an acrylic resin as a binder component and at least one of a brightening material and a coloring pigment, and contains 0.5 to 60 parts by mass of the brightening material and the coloring pigment in solid content per 100 parts by mass of the total solid content of the binder component, the brightening material, and the coloring pigment. The decorative laminated member according to claim 1 or 2.

10. A decorative molded article, characterized in that the decorative laminated member according to claim 1 or 2 is pressure-bonded to the surface of a molded body by insert molding.

Images