JP2016155359A - Decorative molded article and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative molded article capable of forming a colorful image; and to provide a method for producing the same.SOLUTION: In a decorative molded article has decorated thermoplastic sheets formed therein, thermoplastic sheets 1, 4, 8A and 8B have a coloring material receiving layer 3, and a porous film formed of a thermoplastic resin composition or layers 2 and 6. The coloring material receiving layer 3 is decorated by sublimation transfer or melting transfer. A method for producing a decorative molded article includes a step of decorating the coloring material receiving layer 3 in the thermoplastic sheet having the coloring material receiving layer 3 and a porous layer formed of the thermoplastic resin composition by sublimation transfer or melting transfer; and a step of forming the decorated thermoplastic sheet.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative molded body formed by molding a decorated thermoplastic sheet, and a method for producing the same.

  A technology to create a face by creating a mold based on the shape data of the human face, and then molding the mold by bringing a thermoplastic synthetic resin sheet into close contact with the negative pressure applied to the mold surface. Is described in Patent Document 1. In paragraph 0032 of Patent Document 1, it is described that coloring is performed after molding of the face, or coloring of hair, eyes, nose, skin, etc. is performed on the synthetic resin sheet in advance by silk printing.

JP 2005-139593 A

  An object of this invention is to provide the decorative molded body which can form a various image, and its manufacturing method.

  The decorative molded body of the present invention is a decorative molded body in which a decorated thermoplastic sheet is molded, wherein the thermoplastic sheet includes a colorant receiving layer and a porous layer made of a thermoplastic resin composition. And the colorant receiving layer is decorated by sublimation transfer or melt transfer.

  In one aspect of the present invention, the porous layer is a porous film made of a thermoplastic resin composition.

  In one aspect of the present invention, the thermoplastic sheet further includes a sheet-like base material, and the color material receiving layer is provided on the base material via the porous layer.

  In one embodiment of the present invention, the sheet-like substrate is a substrate film made of a thermoplastic resin composition.

  In one embodiment of the present invention, an intermediate layer is provided between at least one of the sheet-like base material and the porous layer and between the porous layer and the colorant receiving layer. This intermediate layer may contain colloidal inorganic fine particles.

  In one aspect of the present invention, the thermoplastic sheet further has a glitter layer.

  The method for producing a decorative molded body of the present invention is a step of decorating the colorant receiving layer of a thermoplastic sheet having a colorant receiving layer and a porous layer made of a thermoplastic resin composition by sublimation transfer or melt transfer. And a step of molding the decorated thermoplastic sheet.

  The decorative molded body provided by the present invention is obtained by molding a thermoplastic sheet having a colorant receiving layer decorated by sublimation transfer or melt transfer. According to this sublimation transfer, an image rich in transparency is formed. Further, according to the melt transfer, a matte tone image having an opaque feeling is formed. Since the porous layer provided on this thermoplastic sheet has a heat insulating effect, it protects the dyes and pigments received in the colorant receiving layer from the heat of the mold and maintains a clear image during molding. Can be expected.

  In the present invention, by providing an intermediate layer containing inorganic fine particles between the porous layer and the colorant receiving layer, the dye is prevented (including suppressed) from transferring to the porous layer side during transfer. The In the present invention, a porous layer may be provided on a sheet-like substrate, or a color material receiving layer may be provided. In this case, the inorganic fine particle-containing intermediate layer can be provided between the porous layer and the substrate, and in this case as well, the dye is prevented from transferring to the substrate.

  In the present invention, by providing the glitter transfer layer, it is possible to form an image further rich in design.

It is typical sectional drawing of the thermoplastic sheet used for manufacture of the decorative molded body which concerns on one Embodiment of this invention. It is a top view of the thermal transfer ink sheet used for manufacture of the decorative molded body which concerns on one Embodiment of this invention. It is typical sectional drawing which follows the III-III line of FIG. It is a typical sectional view of a decorated thermoplastic sheet.

[Thermoplastic sheet]
The thermoplastic sheet used in the present invention has a porous layer and a colorant receiving layer. In one embodiment of the present invention, as shown in FIG. 1A, the thermoplastic sheet 1 includes a porous film 2 as a porous layer made of a thermoplastic resin composition, and a color formed on the porous film 2. And a material receiving layer 3.

  In another aspect of the present invention, as shown in FIG. 1B, the thermoplastic sheet 4 includes a base film 5 made of a thermoplastic resin composition, and a porous layer 6 formed on the base film 5. And a colorant receiving layer 3 formed on the porous layer 6.

  In still another embodiment of the present invention, a base material 9 made of paper or a thermoplastic resin composition is formed on the base material 9 as shown in the thermoplastic sheets 8A and 8B of FIG. 1 (c) or (d). Porous layer 6 and color material receiving layer 3 formed on porous layer 6, and further, between substrate 9 and porous layer 6 or between porous layer 6 and color material receiving It has an intermediate layer 7 formed between the layers 3. The intermediate layer 7 may be provided both between the base material 9 and the porous layer 6 and between the porous layer 6 and the color material receiving layer 3.

  These thermoplastic sheets 1, 4, 8A, and 8B are decorated to the colorant receiving layer 3 by sublimation transfer or melt transfer, and then pressed to a mold by a molding method such as a vacuum molding method to form a predetermined shape. Is done.

  Hereinafter, materials and the like constituting each film and layer will be described.

[Porous film 2]
The porous film 2 in the thermoplastic sheet 1 in FIG. 1A is preferably a porous film containing a polypropylene resin as a base resin and having fine voids inside. A porous film having a thickness in the following range and containing a polypropylene resin can improve the texture of the surface of the printed product of the obtained thermal transfer image-receiving sheet.

The thickness of the porous film 2 is preferably 10 μm or more and 100 μm or less, more preferably 15 μm or more and 80 μm or less, and further preferably 15 μm or more and 40 μm or less. The porous film preferably has a density measured by JIS K6922 of 0.1 g / cm ³ or more and 1.5 g / cm ³ or less, and 0.3 g / cm ³ or more and 1.0 g / cm ³ or less. Is more preferable.

  As a method for producing fine voids in the film, a compound is prepared by kneading organic fine particles or inorganic fine particles (one kind or plural kinds) incompatible with the resin as the base of the film. Microscopically, this compound forms a fine sea-island structure with the base resin and fine particles incompatible with the base resin, and the compound is formed into a film and stretched to form the sea-island interface. The fine voids as described above are generated by the peeling of the film or the large deformation of the region forming the island.

  As a method for forming the fine voids, for example, there is a method of adding polyester or acrylic resin mainly composed of polypropylene and having a melting point higher than that of polypropylene. In this case, polyester or acrylic resin serves as a nucleating agent that forms fine voids. In any case, the content of the polyester and acrylic resin is preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of polypropylene. When the content is 2 parts by mass or more, fine voids can be sufficiently generated, and the printing sensitivity can be further improved. Moreover, when content is 10 mass parts or less, the heat resistance of a porous film can fully be ensured.

  Moreover, when producing the porous film which uses polypropylene as the base resin, it is preferable to add polyisoprene in order to generate finer and dense voids. For example, a porous film having high printing sensitivity can be obtained by preparing a compound composed mainly of polypropylene, blended with acrylic resin or polyester, and polyisoprene, forming a film, and stretching.

  The porous film 2 may be subjected to a surface treatment in order to improve adhesion with the colorant receiving layer 3. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. can do. Only one type of the surface treatment may be applied, or two or more types may be applied.

[Color material receiving layer 3]
The colorant receiving layer 3 in the thermoplastic sheets 1, 4, 8 </ b> A, 8 </ b> B is for receiving a sublimation dye or a dye-containing molten resin transferred from the thermal transfer ink sheet and maintaining the formed image. The resin for forming the colorant receiving layer includes polycarbonate resin, polyester resin, polyamide resin, acrylic resin, cellulose resin, polysulfone resin, polyvinyl chloride resin, polyvinyl acetate resin, and vinyl chloride. -One or two of vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polyurethane resin, polystyrene resin, polypropylene resin, polyethylene resin, ethylene-vinyl acetate copolymer resin, and epoxy resin A thermoplastic resin composed of at least seeds can be mentioned.

  In order to improve releasability from the thermal transfer ink sheet, a release agent may be included in the colorant receiving layer. As release agents, solid waxes such as polyethylene wax, amide wax, fluororesin powder, fluorine or phosphate ester surfactants, various modified silicone oils such as silicone oil, reactive silicone oil, curable silicone oil, And various silicone resins. Silicone oil is preferred. An oily oil can be used as the silicone oil, but a modified silicone oil is preferred. As the modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, aralkyl-modified silicone oil, epoxy-aralkyl-modified silicone oil, alcohol-modified silicone oil, vinyl-modified silicone oil, urethane-modified silicone oil, etc. can be preferably used. Epoxy-modified silicone oil, aralkyl-modified silicone oil, and epoxy-aralkyl-modified silicone oil are particularly preferred. It is also preferable to use a combination of two or more of these release agents. The addition amount of these modified silicone oils is preferably 0.5% by mass or more and 30% by mass or less of the resin constituting the colorant receiving layer.

  In forming the color material receiving layer 3, titanium oxide, zinc oxide, kaolin, clay, calcium carbonate, fine powder silica, etc. are used for the purpose of improving the whiteness of the color material receiving layer and further enhancing the clarity of the transferred image. Pigments and fillers can be added. Moreover, you may add plasticizers, such as a phthalic acid ester compound, a sebacic acid ester compound, and a phosphoric acid ester compound.

The colorant receiving layer 3 comprises a thermoplastic resin and other necessary additives such as mold release agents, plasticizers, pigments, fillers, crosslinking agents, curing agents, catalysts, ultraviolet absorbers, antioxidants, and light. A coating liquid in which a stabilizer or the like is dissolved or dispersed in an organic solvent or water is applied, for example, by a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate, and the above porous film. 2 or a porous layer 6 or an intermediate layer 7 described later, and can be formed by applying and drying. The coating amount of the thus colorant receiving layer thus formed is usually extent 0.5 g / ^{m 2} or more 50 g / ^{m 2} or less in the dry state, preferably 2 g / ^{m 2} or more 10 g / ^{m 2} or less. Such a colorant-receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating.

[Base film 5]
The material of the base film 5 in the thermoplastic sheet 4 in FIG. 1B is polyester such as polyethylene terephthalate, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, acetic acid. Examples of the resin film include one or more of cellulose, ionomer and the like as a main component. These may be used alone, or a laminate in which these are arbitrarily combined may be used. Among these, polyethylene terephthalate, which is an inexpensive general-purpose plastic that can be thinned, is preferable.

  The thickness of the base film 5 can be appropriately selected depending on the material so that the strength, heat resistance, etc. are appropriate, but it is usually preferably about 10 μm to 250 μm, more preferably 50 μm to 150 μm. is there.

  The base film 5 may be subjected to the same surface treatment as that of the porous film 2 in order to enhance the adhesiveness with the porous layer 6.

[Porous layer 6]
The porous layer 6 of the thermoplastic sheets 4, 8 </ b> A, 8 </ b> B of FIGS. 1B to 1D is preferably a porous film, but is formed by applying a coating liquid containing hollow particles. May be. As a porous film, the thing similar to the said porous film 2 can be used. In this case, the thickness of the porous film is preferably about 0.1 to 30 μm, particularly about 8 to 20 μm.

When the porous layer 6 is formed by a coating method, the porous layer may further include coarse particles, a hydrophilic binder, and other additives in addition to the hollow particles. According to a preferred embodiment, the porous layer may be composed of two or more layers. The porous layer has cushioning properties by including hollow particles. Here, the degree of cushioning property of the porous layer can be appropriately adjusted according to the use of the thermal transfer image receiving sheet. The degree of cushioning property of the porous layer can also be adjusted to an arbitrary range by changing the thickness of the porous layer, for example. Density of the porous layer, for example in the range of ^{0.1g / cm 3 ~0.8g / cm 3} , preferably in the range of inter alia ^{0.2g / cm 3 ~0.7g / cm 3} .

  The average particle diameter of the hollow particles used in the present invention is preferably 0.1 to 8 μm, more preferably 0.3 to 5 μm. If the average particle diameter of the hollow particles is in the above range, heat insulation and cushioning properties can be imparted to the hollow layer. In the present invention, the volume average particle diameter of the hollow particles can be measured by a conventionally known method such as the Coulter method (Sysmex FPIA-3000 by Malvern). The average hollowness of the hollow particles is preferably 20% or more, more preferably 30 to 80%. If the average hollowness of the hollow particles is in the above range, heat insulating properties and cushioning properties can be imparted to the porous layer. Furthermore, the organic hollow particle comprised from resin etc. may be sufficient, and the inorganic hollow particle comprised from glass etc. may be sufficient. The hollow particles may be cross-linked hollow particles. In the present invention, commercially available hollow particles can also be used. For example, Ropeke HP-1055, Ropeke HP-91, Ropeke OP-84J, Ropeke Ultra and Ropeke SE (manufactured by Rohm and Haas Co., Ltd.), Nipol MH-5055 (Nippon Zeon Corporation), SX8782 and SX866 (JSR Corporation) are preferred.

  In order to bond the porous film constituting the porous layer 6 and the base film 5, the base film and the porous film are supplied between a pair of rollers together with an adhesive resin melt-extruded between them. In addition, it is preferable to press with a roller. In this case, it is preferable that one roller is a cooling roller (chill roller) and the other roller is a rubber roller.

  The adhesive resin is preferably a thermoplastic resin. Specifically, as a thermoplastic resin, a low density polyethylene resin, a medium density polyethylene resin, a high density polyethylene resin, a linear low density polyethylene resin, a copolymer of ethylene / α-olefin polymerized using a metallocene catalyst Resin, ethylene / polypropylene copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene / acrylic acid copolymer resin, ethylene / ethyl acrylate copolymer resin, ethylene / methacrylic acid copolymer resin, ethylene / methacrylic acid resin Methyl acid copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin are graft-polymerized or copolymerized with ester-forming monomers such as unsaturated carboxylic acid and unsaturated carboxylic acid anhydride Resin, for example, maleic anhydride graft modified with polyolefin resin And the like can be used. These materials can be used alone or in combination.

The adhesive resin is preferably a polyolefin resin having a melting point measured by JIS K7121 of 100 ° C. or higher, and is a polyolefin resin having a melting point of 107 ° C. or higher, particularly 120 ° C. or higher. It is further preferable from the viewpoint of improving the texture. From the viewpoint of improving the curl stability of the thermoplastic sheet and the texture of the decorative surface, the polyolefin resin has a density measured by JIS K6760 of 0.93 g / cm ³ or less, preferably 0.90 g / cm ³ or more. It is preferable that it has a density of 93 g / cm ³ or less, more preferably 0.915 g / cm ³ or more and 0.925 g / cm ³ or less.

  The thickness of the resin layer for adhesion is preferably 2 to 30 μm, particularly preferably 25 to 35 μm.

[Substrate 9]
The base material 9 of the thermoplastic sheets 8A and 8B shown in FIGS. 1C and 1D may be a resin film or paper. As a resin film, the thing similar to the said base film 5 can be used. As the paper substrate, uncoated paper is preferably used, and for example, base paper, photographic base paper, and high-quality paper can be used. For example, high-quality paper or art paper having a basis weight of 78 g / m ² or more and 400 g / m ² or less, preferably 100 g / m ² or more and 200 g / m ² or less can be used. In the present invention, by using uncoated paper as the base material, the cost can be reduced compared to when coated paper is used.

[Middle layer 7]
The intermediate layer 7 is formed between the base material 9 and the porous layer 6 or between the colorant receiving layer 3 and the porous layer 6 in order to prevent dye migration (back-through) to the base material or the porous layer. It is provided between. The intermediate layer 7 preferably contains at least inorganic fine particles. Compared with other particles such as foamed particles, the inorganic fine particles are excellent not only in improving the dispersibility but also in ensuring transparency. In addition, since the inorganic fine particles provide appropriate heat insulation, an effect of increasing the image density of the printed matter can be expected.

  The inorganic fine particles used in the intermediate layer are preferably ultrafine particles of colloidal inorganic pigments, for example, metal silicates such as aluminum silicate and magnesium silicate; alumina or alumina hydrate (alumina sol, colloidal alumina, cationic Conventionally known compounds such as metal oxides such as aluminum oxide or a hydrate thereof, pseudoboehmite, etc., silica or silica sol, magnesium oxide, titanium oxide, carbonates such as magnesium carbonate, and the like can be used. In the present invention, metal oxides and carbonates are preferable, metal oxides are more preferable, alumina or alumina hydrate is more preferable, and alumina sol is particularly preferable because of its high effect of imparting heat resistance and toughness. The intermediate layer may be composed of only one kind of the above-mentioned colloidal inorganic pigment ultrafine particles, or may be composed of two or more kinds of the above-mentioned colloidal inorganic pigment ultrafine particles.

  The average particle size of the colloidal inorganic pigment ultrafine particles is usually 100 nm or less, preferably 50 nm or less, particularly preferably 3 to 30 nm. The average particle diameter can be obtained by a method of directly measuring the size of primary particles from an electron micrograph of a cross section in the thickness direction of the intermediate layer according to the present invention. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle, and the volume (weight) of each particle was determined for 100 or more particles. The volume average particle size is obtained by approximating the particle size to a rectangular parallelepiped, and the average particle size is used. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

The colloidal inorganic pigment ultrafine particles are used for the purpose of facilitating dispersion in a sol form in an aqueous solvent.
A dispersion stabilizer such as acetic acid may be blended and processed into an acidic type, a fine particle charge may be converted into a cation, or a surface treatment may be performed. The colloidal inorganic pigment ultrafine particles may be commercially available products such as alumina sol 100 (manufactured by Nissan Chemical Industries, Ltd.) and alumina sol 200 (manufactured by Nissan Chemical Industries, Ltd.).

  In addition to the inorganic fine particle component described above, a resin component serving as a binder can be added to the intermediate layer. Examples of the resin component include polyester resins, polyacrylate resins, polyurethane resins, styrene acrylate resins, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose butyrate and the like. Examples thereof include resins, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, polyvinyl pyrrolidone resins, and polyvinyl alcohol resins. These resins may be used alone or in combination of two or more.

  It is preferable that the addition amount of said resin component is 0-50 mass% of the total solid of an intermediate | middle layer. When the intermediate layer is formed only from the inorganic fine particle component without using the resin component, generally, an aqueous intermediate layer coating solution composed of colloidal inorganic pigment ultrafine particles is applied onto the substrate or the porous layer and dried. Can be formed. The intermediate layer is more preferably formed by a sol-gel method using an intermediate layer coating solution prepared by dispersing colloidal inorganic pigment ultrafine particles in an aqueous medium. Since such an intermediate layer is formed without using a binder resin, it is excellent in heat resistance and toughness, and also has good adhesion to an adjacent layer. In the above sol-gel method, it is preferable to perform drying by exposure to hot air at 90 to 130 ° C. after coating so that the sol form of the colloidal inorganic pigment ultrafine particles becomes a dry gel.

  The intermediate layer also includes an intermediate layer coating solution in which inorganic fine particles are dispersed in a solvent, and other resin components contained therein are dispersed or dissolved in a solvent. It can also be formed by coating and drying by a conventionally known forming means such as a screen printing method or a reverse roll coating method using a gravure plate.

The intermediate layer can be coated with an intermediate layer coating solution in an amount such that the coating amount after drying is 0.01 to 5 g / m ² , but it is excellent in heat resistance, toughness and the like. it is preferable to coat the intermediate layer coating solution in an amount of coating amount after drying of 0.05 g / ^{m 2} or more 1.0 g / ^{m 2} or less.

  The intermediate layer may be a deposited film of a metal such as aluminum or zinc, or a metal oxide such as silica. The thickness of the deposited film is preferably about 50 to 70 mm.

[Primer layer]
In the thermoplastic sheets 1, 4, 8A, 8B, a primer layer may be provided between the colorant receiving layer and the porous layer. This primer layer is intended to impart adhesion, whiteness, cushioning, concealing, antistatic, and anti-curl properties. The binder resin used for the primer layer is polyurethane resin, polyester resin, polycarbonate resin, polyamide resin, acrylic resin, polystyrene resin, polysulfone resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl chloride- One or two kinds of vinyl acetate copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin, epoxy resin, cellulose resin, ethylene-vinyl acetate copolymer resin, polyethylene resin, and polypropylene resin The above can be mentioned, and those having an active hydroxyl group among these resins can further be used as a cured product thereof.

Moreover, it is preferable to add fillers such as titanium oxide, zinc oxide, magnesium carbonate, and calcium carbonate to the primer layer in order to impart whiteness and concealment. Furthermore, stilbene compounds, benzimidazole compounds, and benzoxazole compounds are added as fluorescent brightening agents to enhance whiteness, and hindered amine compounds and hindered phenol compounds are used to increase the light fastness of printed materials. Add compounds, benzotriazole compounds, benzophenone compounds, etc. as UV absorbers or antioxidants, or add cationic acrylic resins, polyaniline resins, and various conductive fillers to impart antistatic properties can do. The coating amount of the primer layer is preferably about 0.5 g / m ² or more and 5 g / m ² or less in a dry state. The primer layer and the like may be applied by the same method as that for forming the colorant receiving layer.

[Release layer]
The thermoplastic sheets 1, 4, 8 </ b> A, 8 </ b> B may further have a release layer on at least a part of the surface of the color material receiving layer 3. The release layer can be formed by applying the above-described release agent dissolved or dispersed in a suitable solvent as the release agent of the colorant receiving layer 3 and then drying it. Although it does not specifically limit as a mold release agent used for a mold release layer, The reaction hardened | cured material of an amino modified silicone oil and an epoxy modified silicone oil is preferable. The thickness of the release layer is preferably 0.01 μm or more and 5.0 μm or less, and more preferably 0.05 μm or more and 2.0 μm or less. The release layer can also be formed by using silicone oil when forming the colorant receiving layer and curing the silicone oil bleed out on the surface after application.

[Thermal transfer ink sheet]
The thermoplastic sheet 1, 4, 8A, or 8B is used together with the thermal transfer ink sheet to form an image, and decoration is performed. In addition, decoration may be performed so that the location where the back side of a thermoplastic sheet can be seen through, and the location which is not transparent are formed.

  As shown in FIG. 2, the thermal transfer ink sheet 20 is provided with thermal transferable color material layers 22 to 24 and, if necessary, a glitter transfer layer 25 on one surface of the base sheet 21. What has the layer structure by which the heat resistant slipping layer is provided in the other surface is good. Hereinafter, each layer constituting the thermal transfer ink sheet will be described.

[Base material sheet]
As the material of the base sheet 21 constituting the thermal transfer ink sheet, conventionally known materials can be used, and other materials can be used as long as they have a certain degree of heat resistance and strength. can do. For example, polyesters such as polyethylene terephthalate, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, cellulose acetate, resin films such as ionomer, paper such as condenser paper, paraffin paper, Nonwoven fabric etc. are mentioned. These may be used alone, or a laminate in which these are arbitrarily combined may be used. Among these, polyethylene terephthalate, which is an inexpensive general-purpose plastic that can be thinned, is preferable.

  The thickness of the base sheet can be appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but usually it is preferably about 0.5 μm to 50 μm, more preferably 1 μm to 20 μm. More preferably, it is 1 μm or more and 10 μm or less.

  The base sheet may be subjected to a surface treatment in order to improve adhesion with an adjacent layer. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. can do. Only one type of the surface treatment may be applied, or two or more types may be applied.

  Furthermore, it is also possible to apply and form an adhesive layer on the base sheet as an adhesive treatment of the base sheet. An adhesion layer can be formed from the following organic materials and inorganic materials, for example. Examples of the organic material include polyester resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, polyether resins, polystyrene resins, Examples thereof include polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyvinyl pyrrolidone and vinyl resins such as modified products thereof, and polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral. Examples of the inorganic material include silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicion bakumaite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, oxidation Examples thereof include ultrafine particles of colloidal inorganic pigments such as magnesium and titanium oxide.

  Moreover, when manufacturing a plastic film by extending | stretching as said surface treatment, a primer liquid can be apply | coated to an unstretched film and it can also carry out by extending | stretching after that.

[Thermal transferable colorant layer]
The thermal transfer ink sheet 20 is provided with thermal transferable color material layers 22 to 24 on one surface of a base sheet 21. When the thermal transfer ink sheet is a sublimation type thermal transfer ink sheet, a layer containing a sublimation dye is formed as the thermal transferable color material layer, and when the thermal transfer type thermal transfer ink sheet is a hot melt composition containing a colorant A layer containing a heat-meltable ink is formed. When the thermal transfer ink sheet is a sublimation type thermal transfer ink sheet, the thermal transfer color material layers 22 to 24 are a Y dye layer region, an M dye layer region, and a C dye layer region, and further, a K dye layer region is provided. May be. In addition, a layer region containing a sublimable dye and a layer region containing a heat-meltable ink made of a heat-melting composition containing a colorant are provided in a surface sequence on a continuous base sheet. Also good.

  As the material of the heat transferable color material layer, conventionally known dyes can be used, but those having good characteristics as a printing material, for example, having a sufficient coloring density and changing color due to light, heat, temperature, etc. Preferred are diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazomethine, imidazolazomethine, imidazoazomethine, pyridone Azomethine dyes such as azomethine, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzeneazo dyes, pyridoneazo, thiophenazo, iso Thiazoleazo, pyro Azo dyes such as ruazo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, and disazo, spiropyran dyes, indolinospiropyran dyes, fluorane dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone dyes And dyes. Specifically, red dyes such as Disperse Red 60, Disperse Violet 26, CeresRed 7B, Samaron Red F3BS, yellow dyes such as Disperse Yellow 231, PTY-52, Macrolex Yellow 6G, Solvent Blue 63, Waxolin Blue AP-FW, Holon Brilliant Blue S-R, MS Blue 100, C.I. I. And blue dyes such as Solvent Blue 22. In addition, the dye contained in the ribbon used by the sublimation type thermal transfer system marketed can also be used.

  Examples of the binder resin for supporting the dye include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxyethyl cellulose resin, methyl cellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, polyvinyl acetate resin, and polyvinyl butyral resin. And vinyl resins such as polyvinyl acetal resin and polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, and polyester resins. Among these, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable from the viewpoints of heat resistance, dye transferability, and the like.

  Examples of the method for forming the heat transferable color material layer include the following methods. For the heat-transferable colorant layer obtained by adding additives such as a release agent to the dye and binder resin as necessary, dissolving in an appropriate organic solvent such as toluene and methyl ethyl ketone, or dispersing in water. A coating solution (dissolved solution or dispersion) is applied to one surface of a substrate sheet by, for example, a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater, etc., and dried. Let The heat transferable color material layer has a thickness of about 0.2 μm or more and 5.0 μm or less, and the content of the sublimable dye in the heat transferable color material layer is 5 mass% or more and 90 mass% or less, preferably 5 It is preferable that they are mass% or more and 70 mass% or less.

[Brightness transfer layer]
The thermal transfer ink sheet may be provided with a glitter transfer layer 25 on the same surface side as the thermal transfer color material layer. By transferring the glitter transfer layer to the colorant receiving layer of the thermoplastic sheet to form the glitter layer, the surface of the molded body can be decorated with glitter.

  As shown in FIG. 3, the glitter transfer layer 25 can be composed of a release layer 26, a relief forming layer 27, a reflective layer 28, and an adhesive layer 29. Note that the adhesive layer 29 may be omitted.

<Peeling layer>
In order to stabilize and improve transferability at the time of transfer, it is preferable to provide a release layer 26 on the substrate 21. As the resin for the release layer 26, a release resin, a resin containing a release agent, a curable resin that is cross-linked by ionizing radiation, and the like can be used. The releasable resin is, for example, a fluorine resin, silicone, melamine resin, epoxy resin, polyester resin, acrylic resin, fiber resin, wax, melamine resin, or the like. The resin containing the release agent is, for example, an acrylic resin, vinyl resin, polyester resin, or fiber resin obtained by adding or copolymerizing a release agent such as fluorine resin, silicone, or various waxes. is there. The curable resin that is cross-linked by ionizing radiation is, for example, a resin containing a monomer or oligomer having a functional group that is polymerized (cured) by ionizing radiation such as ultraviolet (UV) or electron beam (EB).

  The release layer 26 is provided on one surface of the substrate 21 as necessary. The release layer 26 is formed by dispersing or dissolving the resin in a solvent and using a known printing or coating method such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, It may be applied to at least a part of 21 and dried to form a coating film, or a film may be formed by extrusion coating. Further, it may be crosslinked by heat drying, aging, or irradiation with ionizing radiation.

  The thickness of the release layer 26 is usually about 0.01 to 5.0 μm, preferably about 0.5 to 3.0 μm. The thinner the thickness is, the better. However, when the thickness is 0.1 μm or more, the film forming property is excellent and the peeling force is stable.

<Relief forming layer>
(Relief forming layer material)
As the material of the relief forming layer 27, a thermoplastic resin such as polyvinyl chloride, acrylic resin (eg, polymethyl methacrylate), polystyrene, polycarbonate, or the like, or a thermosetting resin such as unsaturated polyester, melamine, epoxy, or urethane is cured. Ionizing radiation curable such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, triazine acrylate It is possible to use a cured resin, or a mixture of the above thermoplastic resin and thermosetting resin, or ionizing radiation curable resin. In particular, a thermosetting resin excellent in durability such as chemical resistance, light resistance and weather resistance, and a curable resin curable by ionizing radiation such as ultraviolet rays and electron beams are preferable. Preferably, those obtained by curing an ionizing radiation curable resin such as polyester (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate can be used, and urethane-modified acrylate resins are particularly preferable.

(Film formation method of relief forming layer)
The relief forming layer 27 can be formed as follows, for example.
For the above-mentioned materials, for example, an ionizing radiation curable resin of a urethane-modified acrylic resin, if necessary, a photopolymerization initiator, a photosensitizer, a photopolymerization accelerator, a polyfunctional monomer or oligomer, a release agent, Various auxiliary agents such as a polymerization inhibitor, a viscosity modifier, a surfactant, an antifoaming agent, and a polymer such as silicone and styrene-butadiene rubber are blended and dissolved or dispersed in an organic solvent, or A solvent-free composition for a relief forming layer (ink) is obtained without adding a solvent. The relief forming layer composition (ink) is applied onto the release layer 27 or the substrate sheet 21 by, for example, a roll coating method, a gravure coating method, or any other known coating method or printing method, and dried as necessary. do it.
The thickness of the relief forming layer 27 is usually about 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.5 to 2 μm. If the relief forming layer 27 is too thin, the glitter (brightness) is remarkably reduced, and even if the upper limit is exceeded, the brightness is sufficient, which is disadvantageous in terms of cost.

(Relief shape)
The relief shape of the relief forming layer 27 is a concavo-convex shape and is not particularly limited, but preferably has a fine concavo-convex shape and expresses functions such as light diffusion, light scattering, light reflection, and light diffraction. Examples thereof include a Fourier transform, a lenticular lens, a light diffraction pattern, and a moth eye. Further, although there is no light diffraction function, a hairline pattern, mat pattern, line pattern, interference pattern, non-colored pattern, etc., that expresses a unique glitter may be used. As the light diffraction concavo-convex pattern, a hologram or diffraction grating in which interference fringes due to light interference between object light and reference light are recorded in a concavo-convex pattern can be applied. Holograms include laser reproduction holograms such as Fresnel holograms, white light reproduction holograms such as rainbow holograms, color holograms utilizing these principles, computer generated holograms (CGH), and holographic diffraction gratings.

  Examples of the diffraction grating include a holographic diffraction grating using a hologram recording means. In addition, an arbitrary diffraction light can be obtained based on a calculation by mechanically creating a diffraction grating using an electron beam drawing apparatus or the like. There may also be mentioned diffraction gratings. Further, a mechanical cutting method may be used. These holograms and / or diffraction gratings may be recorded single or multiple, or may be recorded in combination. These original plates can be prepared by known materials and methods. Usually, a laser beam interference method using a glass plate coated with a photosensitive material, an electron beam drawing method on a glass plate coated with an electron beam resist material, a machine A cutting method can be applied.

(Shaping the relief forming layer)
A method for shaping the relief forming layer 27 into the above relief shape (also referred to as replication) is as follows.
In the shaping by the hot pressing method, a stamper (metal plate or resin plate) on which a relief is formed is pressure-bonded (so-called embossing) to the surface of the relief forming layer 27, and the relief is shaped to the relief forming layer 27. Then, after duplicating, the stamper is peeled off. The method of commercial duplication is to irradiate ionizing radiation after embossing the surface of the relief forming layer 27 using a mold or resin type stamper and replicating the relief, or irradiating ionizing radiation during embossing. After that, the relief is duplicated by peeling off the stamper. This commercial duplication can be carried out in a long form, allowing continuous duplication work. Further, a relief can be reproduced more commercially by using a cylindrical stamper prepared by attaching a stamper to a cylinder or by directly engraving a relief on the cylinder.

(Relief hardening)
When an ionizing radiation curable resin is used as the material of the relief forming layer 27, the ionizing radiation curable resin is cured by irradiating ionizing radiation during or after embossing with a stamper. The ionizing radiation curable resin becomes an ionizing radiation curable resin (relief-forming layer 27) when it is cured (reacted) by irradiation with ionizing radiation after the relief is formed. The ionizing radiation may be classified according to the quantum energy of the electromagnetic wave, but in this specification, all ultraviolet rays (UV-A, UV-B, UV-C), visible light, gamma rays, X-rays, electrons It is defined as including a line. Accordingly, ultraviolet (UV), visible light, gamma ray, X-ray, electron beam, or the like can be applied as ionizing radiation, but ultraviolet (UV) is preferable, and ultraviolet having a wavelength of 300 to 400 nm is optimal. In the case of ultraviolet curing, an ionizing radiation curable resin that is cured by ionizing radiation is added with a photopolymerization initiator and / or a photopolymerization accelerator. However, in the case of electron beam curing with high energy, these do not need to be added, and if an appropriate catalyst exists, it can be cured with thermal energy.
When a thermosetting resin is used as the material of the relief forming layer 27, it may be cured by aging in a temperature and humidity environment according to the curing conditions of the thermosetting resin to be used.

<Reflective layer>
By providing the reflective layer 28 on the relief surface of the relief forming layer 27 provided with a predetermined relief structure, the reflection and / or diffraction effect of the relief can be enhanced. As a material of the reflective layer 28, for example, a metal or a transparent metal compound having a difference in refractive index can be applied.

  The metal used for the reflective layer 28 is a thin film of a metallic element that has a metallic luster and reflects light, such as metals such as Cr, Ni, Ag, Au, and Al, and their oxides, sulfides, nitrides, etc. A thin film may be used alone or in combination. The light reflective metal thin film can be formed by a vacuum thin film method such as a vacuum deposition method, a sputtering method, or an ion plating method so as to have a thickness of about 10 to 2000 nm, preferably 20 to 1000 nm. In addition, it can be formed by plating. If the thickness of the reflective layer 28 is less than the above range, light is transmitted to some extent and the effect is reduced. If the thickness is above the above range, the reflection effect is not changed, which is wasteful in cost.

Further, as a transparent reflecting layer 28, it has a substantially colorless and transparent hue, and its optical refractive index is different from that of the relief forming layer 27, so that it can visually recognize glitter such as holograms even though there is no metallic luster. Therefore, a bright film such as a transparent hologram can be produced. Examples of such a film include a thin film having a higher refractive index than the relief forming layer 27 and a thin film having a lower refractive index. Examples of the former include ZnS, TiO ₂ , Al ₂ O ₃ , and Sb. ₂ S ₃ , SiO, SnO ₂ , ITO, etc., and examples of the latter include LiF, MgF ₂ , and AlF ₃ . Also, a general light-reflective metal thin film such as aluminum can be used when it has a thickness of 200 mm or less. As with the metal thin film, the transparent metal compound is formed on the relief surface of the relief forming layer 27 by vapor deposition, sputtering, ion plating, CVD, or the like so as to have a thickness of about 10 to 2000 nm, preferably 20 to 1000 nm. It may be provided by a vacuum thin film method or the like. Further, a transparent synthetic resin having a refractive index different from that of the relief forming layer 27 may be used.

<Adhesive layer>
As the material of the adhesive layer 29, a heat-bonding adhesive that is melted or softened by heat and bonded can be used. For example, an ionomer resin, an acid-modified polyolefin resin, an ethylene- (meth) acrylic acid copolymer, ethylene- ( (Meth) acrylic acid ester copolymer, polyester resin, polyamide resin, vinyl resin, acrylic / methacrylic (meth) acrylic resin, acrylic ester resin, maleic acid resin, butyral resin, alkyd Resin, polyethylene oxide resin, phenol resin, urea resin, melamine resin, melamine-alkyd resin, cellulose resin, polyurethane resin, polyvinyl ether resin, silicone resin, rubber resin, etc. are used alone or in combination. be able to. The resin of the adhesive layer 29 is preferably a vinyl resin, an acrylic resin, a butyral resin, or a polyester resin in terms of adhesive strength. More preferable is a maleic acid-vinyl chloride-vinyl acetate copolymer in terms of adhesiveness.
If necessary, additives such as a filler, a plasticizer, a colorant, and an antistatic agent may be appropriately added to the adhesive layer 29.

  The thickness of the adhesive layer 29 is usually about 0.05 to 10 μm, preferably 0.1 to 5 μm. If the thickness of the adhesive layer 29 is less than the above range, the adhesive strength with the transfer medium is insufficient and drops off, and if it exceeds the above range, the adhesive effect is sufficient and the effect does not change, and therefore it is wasteful in cost. Furthermore, the heat of the thermal head is wasted.

[Protective layer]
The thermal transfer ink sheet may be provided with a protective layer in the surface order on the same side as the thermal transferable color material layer. After the color material is transferred to the color material receiving layer of the thermoplastic sheet, the image can be protected from light, gas, liquid, abrasion, etc. by transferring the protective layer and covering the image. Other layers such as an adhesive layer, a release layer, or an undercoat layer may be provided as a protective layer.

[Heat resistant slipping layer]
A heat resistant slipping layer is formed on the surface of the base sheet opposite to the heat transferable color material layer.

  The heat resistant slipping layer is mainly composed of a heat resistant resin. The heat resistant resin is not particularly limited. For example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyether resin, polybutadiene resin, styrene-butadiene copolymer resin, Acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate-hydrodiene Phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, Fine chlorinated polyolefin resins.

  The heat resistant slipping layer may be formed by blending additives such as a slipperiness imparting agent, a crosslinking agent, a release agent, an organic powder, and an inorganic powder in addition to the above heat resistant resin.

  The heat resistant slipping layer is generally a coating solution for the heat resistant slipping layer by adding the above-mentioned heat resistant resin, and optionally adding the above-mentioned slipperiness imparting agent and additives to the solvent and dissolving or dispersing each component. Then, the coating solution for heat resistant slipping layer can be applied on a base sheet and dried. As the solvent in the heat-resistant slipping layer coating solution, the same solvent as the solvent in the heat transferable colorant layer coating solution described above can be used.

Examples of the coating method for the coating solution for the heat resistant slipping layer include wire bar coating, gravure printing, screen printing, reverse roll coating using a gravure plate, and gravure coating is particularly preferable. The heat-resistant slipping layer coating solution may be applied so that the dry coating amount is preferably 0.1 g / m ² or more and 3 g / m ² or less, more preferably 1.5 g / m ² or less.

[Decoration process]
The above-described thermoplastic sheet and the above-described thermal transfer ink sheet are superposed and heated according to a recording signal, whereby the thermal transfer color material layer of the thermal transfer ink sheet, and further the glitter transfer layer, are converted into a thermoplastic sheet. It is possible to decorate by forming an image by transferring it to the colorant receiving layer. In the present invention, an image can also be formed by high-speed printing. Here, the high-speed printing is 0.5 msec / line or more and 3.0 msec / line or less.

  As a thermal transfer recording apparatus that can be used for such image forming decoration, a known apparatus can be used and is not particularly limited. In the present invention, a commercially available thermal transfer recording apparatus can be used, and examples thereof include a sublimation thermal transfer printer (manufactured by ALTECH ADS (model: MEGAPICEL III), manufactured by DNP Photo Lucio (model: DS40)).

  As shown in FIG. 4, the image-formed product 30 obtained in the decorating step forms a thermal transfer image on the colorant receiving layer 32 of the thermoplastic sheet 31 using the thermal transfer sheet ink 20 described above. A glittering layer is formed on the surface where the thermal transfer image surface and / or the thermal transfer image surface is not formed, and a protective layer 33 is further formed as necessary. The thermoplastic sheet 31 is any one of the thermoplastic sheets 1, 4, 8 </ b> A, and 8 </ b> B, and the color material receiving layer 32 is the color material receiving layer 3. In the case of the sublimation type thermal transfer ink sheet, the dye is transferred into the color material receiving layer 32 of FIG. Although illustration is omitted, in the case of a heat melting type thermal transfer ink sheet, a dye- or pigment-containing resin layer is formed on the surface of the colorant receiving layer 32.

[Molding process]
After the decorative thermoplastic sheet manufactured as described above is installed so that the decorative surface side faces the molding surface of a molding die (for example, a mold) having a molding surface of a predetermined shape, Heat and soften the decorative sheet. Thereafter, the decorative thermoplastic sheet is molded by vacuum suction from the mold side and bringing the softened decorative thermoplastic sheet into close contact with the molding surface of the mold. The forming method may be a method other than vacuum forming.

[Use]
In addition to decorative items such as masks, the present invention provides various kinds of miscellaneous goods such as housings for home appliances, electronic / electrical devices, OA devices, communication devices, building materials, playground equipment, toys, accessories, stationery, etc. It can be employed in resin products and their manufacture.

1, 4, 8, 8A, 8B Thermoplastic sheet 2 Porous film 3 Colorant receiving layer 5 Base film 6 Porous layer 7 Intermediate layer 9 Base material

Claims (8)

In the decorative molded body in which the decorated thermoplastic sheet is molded,
The thermoplastic sheet has a colorant receiving layer and a porous layer made of a thermoplastic resin composition,
The decorative molded body, wherein the colorant receiving layer is decorated by sublimation transfer or melt transfer.   The decorative molded body according to claim 1, wherein the porous layer is a porous film made of a thermoplastic resin composition.   The said thermoplastic sheet further has a sheet-like base material, The said color material receiving layer is provided on this base material through the said porous layer, The Claim 1 or 2 characterized by the above-mentioned. Decorative molded body.   4. The decorative molded body according to claim 3, wherein the substrate is a substrate film made of a thermoplastic resin composition.   5. The additive according to claim 3, wherein an intermediate layer is provided between at least one of the base material and the porous layer and between the porous layer and the colorant receiving layer. Decorative molded body.   The decorative molded body according to claim 5, wherein the intermediate layer contains colloidal inorganic fine particles.   The decorative molded body according to any one of claims 1 to 6, wherein the thermoplastic sheet further includes a glitter layer. Decorating the coloring material receiving layer of the thermoplastic sheet having a coloring material receiving layer and a porous layer made of a thermoplastic resin composition by sublimation transfer or melt transfer;
A process for producing a decorative molded body, comprising a step of molding the decorated thermoplastic sheet.

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