JP2013208858A - Thermal transfer foil and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide thermal transfer foil in which the durability of a decorative layer of a decorative molding article is improved, and to provide a manufacturing method thereof.SOLUTION: Thermal transfer foil has a substrate, a non-patterned layer, and a coloring material layer on one surface of the substrate in this order. The coloring material layer covers a non-patterned portion of the non-patterned layer, and an circumferential edge portion of the coloring material layer does not contact with the circumferential edge thermally transferred to a body to be transferred.

Description

  The present invention relates to a thermal transfer foil and a method for producing the same, and more particularly, a thermal transfer foil comprising a base material, a punched pattern layer, and a color material layer in this order on one surface of the base material, and It relates to the manufacturing method.

  Conventionally, in fields such as household appliances, automobile interior parts, and miscellaneous goods, the surface of a resin molded body, which is a transfer object, is decorated with letters and patterns with white, black, and color inks. Has developed functionality and design.

  In particular, an injection molding simultaneous decorating method has been used for decorating a resin molded body having a complicated surface shape such as a three-dimensional curved surface. The injection molding simultaneous decorating method is a resin molded body in which a decorative sheet inserted into an in-mold mold during injection molding is integrated with a molten injection resin injected and injected into a cavity. It is a method of decorating the surface of the. Furthermore, depending on the difference in the configuration of the decorative sheet integrated with the resin molded body, it is generally divided roughly into an injection molding simultaneous laminate decoration method and an injection molding simultaneous transfer decoration method.

  In the injection molding simultaneous transfer decoration method, the transfer layer side of the transfer foil for injection molding simultaneous transfer decoration is arranged facing the inner side of the mold and heated from the transfer layer side by a hot platen. Mold to conform to the in-mold shape. Next, the molten injection resin is injected into the cavity, and the transfer foil and the injection resin are integrated. And after cooling a resin molding and taking out from a metal mold | die, the resin molding which has the decorating layer which transferred the transfer layer can be obtained by peeling the base material sheet of this transfer foil (for example, Patent Document 1).

  The resin molded product having a decorative layer thus obtained (decorated molded product) has recently been marketed in addition to the fields of household electrical appliances, automobile interior products, and miscellaneous goods used in the past. For example, it is also attracting attention for use in fields such as notebook personal computers and mobile phones including mobile personal computers. In these fields, it is required to solve various problems that could not be realized by forming an ink layer by a conventionally known printing method (gravure printing, silk screen printing, etc.). For example, in the case of gravure printing, plate making and printing steps are required over many steps, and it is difficult to cope with production in a small lot and a variety of products. In the case of silk screen printing, there is a problem that it takes time to dry the ink, there is a risk of poor appearance due to plate clogging and the like, and insufficient design expression such as gradation.

  In view of this, it has been performed to enhance the design by making the contrast of the pattern stand out by superimposing a blank pattern formed of black food ink and a solid image formed of silver or the like. For example, as shown in FIG. 1, in a conventional thermal transfer foil, a color material layer 20 has been provided on the entire surface of the punched pattern layer 10.

Japanese Patent No. 3793443

  However, as shown in FIG. 1, the color material layer 20 covers the pattern portion 11 of the pattern layer 10, and the peripheral portion 30 of the color material layer 20 is thermally transferred to the thermal transfer body (inside the dotted line) The problem is that the peripheral edge of the color material layer after thermal transfer may be exposed to the outside and the durability of the decorative layer of the decorative molded product is reduced. The inventors have found out.

  The present invention has been made in view of the above-mentioned background art and newly discovered problems, and its purpose is to provide a thermal transfer foil capable of improving the durability of a decorative layer of a decorative molded product and a method for producing the same. It is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in a thermal transfer foil having a base material and a pattern layer and a color material layer in this order on one surface of the base material. By adjusting the area of the color material layer so as to cover the pattern portion of the pattern pattern layer and so that the peripheral edge portion of the color material layer does not contact the peripheral edge portion of the area to be thermally transferred to the transfer object (See FIG. 2), it has been found that the above problems can be solved. Specifically, as shown in FIG. 2, a color material layer 20 is provided on a part of the punched pattern layer 10 in the thermal transfer foil. The color material layer 20 covers the pattern portion 11 of the pattern layer 10, and the peripheral portion 30 of the color material layer 20 is not in contact with the peripheral portion 50 of the region 40 (the inner portion of the dotted line) that is thermally transferred to the thermal transfer body. As a result, it was found that the above-mentioned problems can be solved, and the present invention has been completed.

That is, according to one aspect of the present invention,
A heat transfer foil comprising a base material, and a punched pattern layer and a color material layer in this order on one surface of the base material,
There is provided a thermal transfer foil in which the color material layer covers a pattern portion of the pattern pattern layer, and a peripheral portion of the color material layer does not contact a peripheral portion of a region to be thermally transferred to a transfer target.

  In the aspect of the present invention, it is preferable that the color material layer includes a color material that can be corroded by an acidic chemical and / or an alkaline chemical.

  In the aspect of the present invention, the color material layer preferably includes a color material including at least one selected from the group consisting of aluminum, chromium, gold, silver, and copper.

  In the embodiment of the present invention, it is preferable that the color material layer contains a pigment having an average particle diameter of 1.0 μm or more.

  In the aspect of the present invention, it is preferable that the above-described punched pattern layer is black.

  In the aspect of the present invention, the thermal transfer foil includes a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in this order from the substrate side between the substrate and the punched layer. It is more preferable to have.

  In an embodiment of the present invention, the hard coat layer includes an ionizing radiation curable resin, the anchor coat layer includes a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate, and the receiving layer described above. Preferably comprises a thermoplastic resin.

  In the aspect of the present invention, it is preferable that an adhesive layer is further provided on the color material layer.

  In the embodiment of the present invention, it is preferable that an antistatic layer is further provided on the other surface of the substrate.

According to another aspect of the present invention,
There is provided a decorative molded article having a transferred object and a decorative layer formed by transferring the thermal transfer foil on the transferred object.

According to another aspect of the present invention,
The following steps (1) to (3):
(1) A step of preparing a transparent foil having a base material and a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in this order on one surface of the base material;
(2) preparing a base sheet and an ink ribbon having a release layer and an ink layer in this order on one surface of the base sheet;
(3) A step of forming a pattern layer on the receptor layer on the receptor layer of the transparent foil by a thermal transfer printer using the ink ribbon, and subsequently forming a color material layer on the pattern layer The color material layer is formed so as to cover the pattern portion of the pattern layer and the peripheral portion of the color material layer is not in contact with the peripheral portion of the region to be thermally transferred to the transfer target. A process for producing a thermal transfer foil, comprising the steps of:

According to another aspect of the present invention,
The following steps (4) to (7):
(4) preparing a thermal transfer foil manufactured by the above thermal transfer foil manufacturing method;
(5) inserting the thermal transfer foil into an in-mold mold,
(6) a step of injecting and injecting molten injection resin into the mold;
(7) A method for producing a decorative molded product is provided, which includes a step of integrating the thermal transfer foil and the injection resin to form a decorative layer on the surface of the resin molded body.

According to another aspect of the present invention,
The following steps (8) to (10):
(8) a step of preparing a thermal transfer foil manufactured by the above method of manufacturing a thermal transfer foil;
(9) contacting the thermal transfer foil on the molded resin body;
(10) a step of performing roll transfer by thermal pressure while abutting,
There is provided a method for producing a decorative molded article, comprising:

  According to the present invention, in a thermal transfer foil having a base material, a punched pattern layer, and a color material layer in this order on one surface of the base material, the peripheral edge of the region to be thermally transferred to the thermal transfer body By adjusting the area of the color material layer so as not to contact the part, the peripheral part of the color material layer after thermal transfer is not exposed to the outside, and the durability of the decorative layer of the decorative molded product is improved. be able to.

It is a schematic conceptual diagram which shows the punched pattern layer and color material layer of the conventional heat transfer foil. It is a schematic cross section which shows an example of the punched pattern layer and color material layer of the thermal transfer foil by this invention. It is a schematic cross section which shows an example of the thermal transfer foil by this invention. It is a schematic cross section which shows an example of the ink ribbon used for manufacture of the thermal transfer foil by this invention. It is a schematic cross section which shows an example of the transparent foil used for manufacture of the thermal transfer foil by this invention.

Thermal transfer foil The thermal transfer foil according to the present invention comprises a substrate, and at least a release layer, a hard coat layer, an anchor coat layer, a receiving layer, and a decoration layer on one surface of the substrate. It has in order. The thermal transfer foil may further have an adhesive layer on the decorative layer. Moreover, you may further have an antistatic layer on the other surface of a base material. According to one aspect of the present invention, the layer structure is formed in the order of antistatic layer / base material / release layer / hard coat layer / anchor coat layer / receptor layer / removal pattern layer / coloring material layer / adhesive layer. A thermal transfer foil is provided. The thermal transfer foil of the present invention is suitably used for injection molding such as in-mold molding and insert molding of decorative molded products, or for roll transfer.

  FIG. 3 shows a schematic cross-sectional view of an example of the thermal transfer foil according to the present invention. The thermal transfer foil 110 shown in FIG. 3 has a release layer 130, a hard coat layer 140, an anchor coat layer 150, a receiving layer 160, a punched pattern layer 170, a color on one surface of the substrate 120. The material layer 180 and the adhesive layer 190 are laminated in this order, and the antistatic layer 210 is formed on the other surface (the side opposite to the receiving layer 160) of the substrate 120. In the manufacturing process of the decorative molded product, the transferred transfer layer 220 includes a hard coat layer 140, an anchor coat layer 150, a receiving layer 160, a punched pattern layer 170, a color material layer 180, and an adhesive layer. The release sheet 230 to be peeled off 190 includes an antistatic layer 210, a base material 120, and a release layer 130. Hereinafter, each layer constituting the thermal transfer foil will be described.

Base material of base material thermal transfer foil is polyolefin resin such as polyethylene and polypropylene, polyvinyl resin such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, Polyester resins such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, acrylonitrile / butadiene / styrene Polymers, cellulose triacetate, cellophane, polycarbonate, polyurethane resins and other elastomer resins are used. Of these, polyester resins, particularly polyethylene terephthalate (hereinafter sometimes referred to as “PET”) are preferred from the viewpoint of good moldability and releasability. The thickness of the substrate is preferably in the range of 25 to 150 μm, more preferably in the range of 38 to 100 μm, from the viewpoints of moldability, shape followability, and easy handling.

The release layer of the release layer thermal transfer foil has at least a hard coat layer, an anchor coat layer, a receiving layer, and a decorative layer, and preferably a transfer layer further having an adhesive layer peels off from the substrate. It is a layer provided for easy execution. By providing the release layer, the transfer layer is reliably and easily transferred from the thermal transfer foil of the present invention to the transfer target, and the release sheet having the antistatic layer, the base material, and the release layer is reliably peeled off. be able to. The release agent used for the release layer includes melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent. A mold release agent such as a mold release agent, a paraffin release agent, an acrylic resin release agent, and a composite release agent thereof is preferable. Among these, acrylic resin-based release agents and polyolefin resin-based release agents are preferable, and those obtained by combining these such as acrylic-polyethylene are particularly preferable.

  Furthermore, the release layer is an ink prepared by dissolving or dispersing in a suitable solvent the additives necessary for the release agent described above, and using a gravure coating method, roll coating method, comma coating method, gravure printing It can be formed by applying and drying by a known means such as a method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the release layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 1 to 5 μm.

Hard coat layer The hard coat layer of the thermal transfer foil becomes the outermost layer of the decorative molded product after the transfer layer is transferred from the thermal transfer foil to the resin molded product, and the molded product or decorative layer is removed from wear, light, chemicals, etc. It is a layer for protection. The hard coat layer preferably contains an ionizing radiation curable resin, and is preferably formed using a polymer having an ionizing radiation curable functional group. Ionizing radiation curable is one having an energy quantum that can crosslink and polymerize molecules in electromagnetic waves or charged particle beams, that is, it is crosslinked by causing polymerization reaction by being excited by irradiation with ultraviolet rays or electron beams. It is the ability to cure. The ionizing radiation curable functional group is a functional group capable of expressing the ionizing radiation curable property, and is at least selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, and an epoxy group. One type.

  The hard coat layer is a reaction having a polymer having at least one selected from a vinyl group, a (meth) acryloyl group, an allyl group, and an epoxy group as an ionizing radiation-curable functional group, and a reactive functional group on the surface of the inorganic particles. It is preferable that the ink composition is formed from an ink composition containing functional inorganic particles and / or reactive irregularly shaped inorganic particles and a polyfunctional isocyanate. This ink can be formed by applying and drying by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.

  Examples of the polymer having an ionizing radiation curable functional group include acrylic (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate, Those obtained by polymerizing urethane (meth) acrylate are preferred. In the present invention, these polymers may be used alone or in combination of two or more.

  The polymer having an ionizing radiation curable functional group has a weight average molecular weight of about 5000 to 150,000, preferably 20,000 to 100,000. When the number average molecular weight is within the above range, the thixotropy of the ink composition can be obtained, and good moldability can be obtained. Here, the number average molecular weight is a value measured by gel permeation chromatography (GPC), and is a value measured under conditions using polystyrene as a standard sample. Moreover, from the viewpoint of obtaining excellent high hardness and scratch resistance, the double bond equivalent of the polymer is 50 to 1000, preferably 100 to 1000, and more preferably 100 to 500. Here, the double bond equivalent means the molecular weight per ionizing radiation-curable functional group.

  Reactive inorganic particles and reactive irregularly shaped inorganic particles have reactive functional groups on the surface of the inorganic particles. Preferred examples of the reactive functional group include a vinyl group, a (meth) acryloyl group, an allyl group, an epoxy group, and a silanol group. From the viewpoint of improving high hardness and scratch resistance, a vinyl group, (meth) An acryloyl group and an allyl group are more preferable.

  Preferred inorganic particles include metal oxide particles such as silica particles (colloidal silica, fumed silica, precipitated silica, etc.), alumina particles, zirconia particles, titania particles, zinc oxide particles, etc., and high hardness and scratch resistance. From the viewpoint of improving the properties, silica particles are preferred.

  Examples of the shape of the inorganic particles include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. These shapes are preferably uniform and sized, and the inorganic particles have a weak interaction with each other. Monodispersed particles are preferred. The average particle diameter of the inorganic particles can be appropriately selected depending on the thickness of the layer formed from the ink composition, but is usually preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.1 μm. Here, the average particle diameter is a 50% particle diameter (d50: median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is expressed as a cumulative distribution. It can be measured using a meter (made by Nikkiso Co., Ltd.).

  The irregular shaped inorganic particles are composed of a group of inorganic particles in which the inorganic particles are connected and aggregated having an average number of connections of 2 to 40. Connected aggregation may be regular or irregular. As the inorganic particles forming the inorganic particle group, inorganic particles composed of metal oxides such as silica (colloidal silica, fumed silica, precipitated silica, etc.), alumina, zirconia, titania, zinc oxide are preferably mentioned. From the viewpoint of improving hardness and scratch resistance, inorganic particles made of silica are preferable. That is, it is preferable that the irregular shaped inorganic particle is composed of a silica particle group in which silica particles are connected and aggregated having an average number of connections of 2 to 40.

  Preferred examples of such reactive irregularly shaped inorganic particles include irregularly shaped inorganic particles whose surface is decorated with a silane coupling agent. Examples of the silane coupling agent include known silane coupling agents having an alkoxy group, an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group, and the like, and more specifically, γ-aminopropyltriethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like are preferable, and γ-methacryloxypropyltrimethoxysilane is more preferable. Γ-methacryloxypropylmethyldimethoxysilane and γ-methacryloxypropyldimethylmethoxysilane.

  There are no particular restrictions on the method of decorating the irregularly shaped inorganic particles with the silane coupling agent, and any known method may be used. A dry method in which the silane coupling agent is sprayed, or after the irregularly shaped inorganic particles are dispersed in the solvent, Examples thereof include a wet method in which a coupling agent is added and reacted.

  The content of reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is preferably 15 to 60% by mass, more preferably 20 to 50% by mass. Here, the content of the reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is such that the reactive inorganic particles and / or the reaction with respect to the total of the polymer and the reactive inorganic particles and / or reactive irregularly shaped inorganic particles. The polymer is a solid content. When the content of the reactive inorganic particles is within the above range, excellent high hardness and scratch resistance can be obtained.

  The ink composition may contain a solvent for the purpose of adjusting the viscosity. Solvents include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone, diacetone alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide; Ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dioxolane; methylene chloride, chloroform Preferred are halogenated hydrocarbons such as chloromethane, trichloroethane and tetrachloroethane; other substances such as dimethyl sulfoxide and propylene carbonate; or a mixture thereof. More preferred solvents include methyl ethyl ketone and methyl isobutyl ketone.

  The amount of the solvent in the ink composition may be appropriately selected according to the viscosity of the composition, but the solid content of the polymer, reactive inorganic particles and reactive irregularly shaped inorganic particles, and other photopolymerization initiators described later. The amount of the solid content is generally about 10 to 50% by mass, preferably 20 to 40% by mass.

  The ink composition can contain a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenone series, ketone series, benzophenone series, benzoin series, ketal series, anthraquinone series, disulfide series, thioxanthone series, thiuram series, and fluoroamine series. Of these, acetophenone, ketone, and benzophenone are preferred. These photopolymerization initiators can be used alone or in combination of two or more.

  The content of the photopolymerization initiator is preferably about 0.5 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 3 to 8%, based on the total of the above polymer and inorganic particles. The polymer and inorganic particles are based on solid content.

  The ink composition may contain various additives depending on the desired physical properties to be obtained. Examples of additives include ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, and antifoaming agents. Agents, fillers and the like.

  Usually, the thickness of the hard coat layer is preferably in the range of 0.5 to 30 μm, and more preferably in the range of 3 to 15 μm. When the thickness of the hard coat layer is within the above range, surface properties such as excellent high hardness, scratch resistance, chemical resistance, and contamination resistance can be obtained, and further excellent moldability and shape followability can be obtained. Can be obtained.

Anchor coat layer The anchor coat layer of the thermal transfer foil is a layer provided to improve the adhesion between the hard coat layer and the receiving layer. The anchor coat layer preferably contains a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate and a thermoplastic resin. Examples of the thermoplastic resin include acrylic resins, polyester resins, cellulose derivative resins, polyvinyl acetal resins, polyvinyl butyral resins, vinyl chloride-vinyl acetate copolymers, and chlorinated polyolefin resins. By forming an anchor coat layer with a urethane resin, which is a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate, and a thermoplastic resin, at least a part of the polyfunctional isocyanate of the anchor coat layer and the acrylic polyol of the receiving layer Alternatively, it can react with or stick to at least a part of the thermoplastic resin to improve the adhesion between the anchor coat layer and the receiving layer. Also, the affinity between the ionizing radiation curable resin of the hard coat layer and the resin (urethane resin) obtained by reacting the acrylic polyol and polyfunctional isocyanate of the anchor coat layer, the thermoplastic resin of the anchor coat layer and the thermoplastic of the receiving layer Due to the affinity with the resin, the adhesion between the hard coat layer, anchor coat layer, and receptor layer can be improved.

  The blending amount of each component in the ink for forming the anchor coat layer is preferably 50 to 80% by mass, more preferably 50 to 75% by mass of acrylic polyol, and preferably 10 to 30% by mass of polyfunctional isocyanate. More preferably, the content is 15 to 25% by mass, and the thermoplastic resin is preferably more than 0% by mass and 30% by mass or less, more preferably 5 to 30% by mass, and further preferably 7 to 25% by mass. When the blending amount of the polyfunctional isocyanate is 10% by mass or more with respect to the total of the acrylic polyol, the polyfunctional isocyanate, and the thermoplastic resin, sufficient adhesion can be obtained. Moreover, when the compounding quantity of polyfunctional isocyanate is 10 mass% or more, 0 mass% may be sufficient as content of the thermoplastic resin in an anchor coat layer.

  Furthermore, the anchor coat layer is an ink prepared by dissolving or dispersing an additive obtained by adding the necessary additives to the above resin, gravure coating method, roll coating method, comma coating method, gravure printing method, It can be formed by applying and drying by known means such as a screen printing method and a gravure reverse roll coating method. Usually, the thickness of the anchor coat layer is preferably in the range of 0.1 to 6 μm, and more preferably in the range of 1 to 5 μm.

Since the receiving layer of the receiving layer thermal transfer foil cannot be directly printed on the anchor coat layer, the receiving layer is for forming and holding on the receiving layer an ink layer transferred from the ink ribbon at the time of pattern formation by thermal transfer. Since adhesion to the anchor coat layer and adhesion to the heat transferable multicolor ink forming the decoration layer are required, it is preferable to use a resin having affinity for both the anchor coat layer and the decoration layer. Therefore, it is preferable that the receiving layer contains an acrylic polyol and a thermoplastic resin. Examples of the thermoplastic resin include acrylic resins, polyester resins, cellulose derivative resins, polyvinyl acetal resins, polyvinyl butyral resins, vinyl chloride-vinyl acetate copolymers, and chlorinated polyolefin resins. By using the same thermoplastic resin as the anchor coat, the adhesion between the anchor coat layer and the receiving layer can be further improved.

  Furthermore, the receiving layer is prepared by dissolving or dispersing the above-mentioned resin with the necessary additives in an appropriate solvent, and using a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen It can be formed by applying and drying by known means such as a printing method and a gravure reverse roll coating method. Usually, the thickness of the receiving layer is preferably in the range of 0.05 to 3.0 μm, more preferably in the range of 0.1 to 1.0 μm, and 0.2 to 0.7 μm. More preferably, it is within the range.

Decorative layer (pattern removal layer and color material layer)
The decorative layer of the thermal transfer foil (sometimes referred to as the “decorative layer” by combining the pattern removal layer and the color material layer) is a layer provided to impart the design properties of the thermal transfer foil. It is a pattern layer that expresses the design of More specifically, the pattern includes wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, stripe pattern and gradation pattern. According to a preferred embodiment, the ink layer is formed by being transferred by a thermal transfer printer using an ink ribbon having an ink layer. By forming the decoration layer by thermal transfer in this way, it is possible to deal with the manufacture of many kinds of small lots and to express complicated designs such as gradation. In addition, the image to be printed is only an image processing process using digital information, and the processes such as general plate making and printing are not required, and the delivery time is shortened by reducing the number of processes and the cost is reduced by not requiring equipment. be able to.

  In the thermal transfer foil according to the present invention, the pattern can be formed by superimposing the punched pattern layer and the color material layer. The color material layer covers the pattern portion of the pattern layer, and the color material layer is formed so that the peripheral portion of the color material layer is not in contact with the peripheral portion of the region to be thermally transferred to the thermal transfer member. The peripheral part of this is not exposed to the outside, and the durability of the decorative layer of the decorative molded product can be improved.

  The colorant of the ink used for forming the colorant layer is a colorant that can be corroded by acidic chemicals and / or alkaline chemicals, preferably at least one selected from the group consisting of aluminum, chromium, gold, silver, and copper. It is also possible to use a color material containing silver, more preferably a silver color material containing aluminum and / or silver. In addition, a pigment having an average particle diameter (d50) of 1.0 μm to 10 μm, preferably 1.5 μm to 5 μm may be used. When such a color material or pigment is used, the durability when exposed to the outside may be reduced. However, in the present invention, even if such a color material or pigment is used, the color material layer after the thermal transfer is used. Since the peripheral edge is not exposed to the outside, the decorative layer of the decorative molded product can have sufficient durability.

  As a colorant for the ink used for forming the punched pattern layer, a black color material, preferably a color material containing carbon black, may be used. By using such a color material, the contrast of the pattern can be emphasized.

  In addition to the color materials and pigments described above, titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue titanium yellow, yellow lead, carbon Inorganic pigments such as black, isoindolinone yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, indanthrene blue RS, aniline black and other organic pigments (including dyes), aluminum, brass and other metals Metal pigments made of powder, titanium dioxide-coated mica, pearlescent pigments made of foil powder such as basic lead carbonate, fluorescent pigments and the like may be used alone or in combination of two or more.

  Examples of the resin of the ink used for forming the pattern layer and the color material layer include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, and polyvinyl acetate. Resins, vinyl chloride-vinyl acetate copolymer resins (vinyl acetate resin), polyvinyl butyral resins, polyvinyl acetal resins, vinyl resins such as polyvinyl pyrrolidone, acrylics such as poly (meth) acrylates and poly (meth) acrylamides Examples thereof include resins, polyurethane resins, polyamide resins, and polyester resins. In the present invention, these resins may be used alone or in combination of two or more. Among these, from the viewpoints of heat resistance, colorant migration, and the like, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable, and a mixed resin of an acrylic resin and a vinyl acetate-based resin is preferable. Particularly preferred. In addition to the binders made of the above-mentioned various resins, the ink used is appropriately mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents.

  The color material layer may be a metal thin film layer or the like. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. Alternatively, a combination thereof may be used. The metal thin film layer may be provided on the entire surface or partially in a pattern.

  The decorative layer may be a layer in which a concealing layer is further provided on the color material layer. The concealing layer is provided for the purpose of concealing the pattern or coloring of the ground (molded product) after the thermal transfer foil is transferred to the decorative molded product. For this reason, the layer configuration after transfer to the molded body is preferably (surface side) decorative layer (extracted pattern layer / coloring material layer / shielding layer) / adhesive layer (molded body side). The shielding layer is usually formed as a full-color or partially solid colored layer without a pattern. In some cases, the cut pattern layer or the color material layer also serves as a solid layer (shielding effect). In this case, the shielding layer may not be formed. The shielding layer can be formed using an ink containing a coloring pigment similar to the pattern layer.

  Usually, the thickness of a decoration layer becomes like this. Preferably it is 0.5-40 micrometers, More preferably, it is 1-15 micrometers. When the thickness of the decoration layer is within the above range, a sufficient thickness can be secured to express a complicated design such as gradation.

The adhesive layer of the adhesive layer thermal transfer foil is a layer for transferring the decorative layer to the resin molded body with good adhesiveness. In the present invention, the adhesive layer preferably contains a resin and may further contain an additive or the like. As the resin used for forming the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the resin molding can be appropriately selected and used. For example, when the material of the resin molding is a polyphenylene oxide-polystyrene resin, a polycarbonate resin, and a styrene resin, an acrylic resin, a polystyrene resin, and a polyamide resin that have an affinity for these resins Is preferably used. Moreover, when the material of the resin molding is a polypropylene resin, it is preferable to use chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, cyclized rubber, coumarone indene resin, or the like.

  Furthermore, the adhesive layer is prepared by dissolving or dispersing the above-mentioned resin with the necessary additives in an appropriate solvent, and using gravure coating, roll coating, comma coating, gravure printing, screen It can be formed by applying and drying by known means such as a printing method and a gravure reverse roll coating method. Usually, the thickness of the adhesive layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 1 to 5 μm.

  In addition, when a decoration layer has sufficient adhesiveness with respect to a resin molding, it is not necessary to provide an adhesive layer. In the present invention, when the ink layer of the ink ribbon is transferred, the release layer in contact with the ink layer may be transferred at the same time, and the release layer may serve as an adhesive layer. Also in this case, it is not necessary to provide a separate adhesive layer.

Antistatic Layer The antistatic layer of the thermal transfer foil is a layer formed to prevent foreign matter from adhering to the transfer foil in the manufacturing process of the decorative molded product, particularly the transfer process. In the present invention, the antistatic layer is made of a metal such as aluminum, gold, silver, copper, or nickel, a metal oxide such as tin oxide, indium oxide, tin oxide-doped indium oxide (ITO), or a conductive material made of graphite. Powder or fine flakes, or a conductive polymer, and may further contain an additive such as a surfactant.

Further, the antistatic layer is prepared by dissolving or dispersing an ink obtained by adding a necessary additive such as a surfactant to the above-mentioned conductive material in an appropriate solvent, using a gravure coating method, a roll coating method, a comma coating. It can be formed by applying and drying by known means such as a coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the antistatic layer is preferably in a range in which a surface resistance value of 10 ⁹ to 10 ¹² Ω / □ is expressed.

  In the present invention, various known solvents can be used for the ink for forming each layer, and they can be appropriately selected and combined according to properties such as a target viscosity. For example, as solvents, hydrocarbons such as toluene and xylene, methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve and other alcohols, acetone, methyl ethyl ketone, Contains ketones such as methyl isobutyl ketone, cyclohexanone, diacetone alcohol, esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, nitrogen such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide Compounds, ethers such as propylene glycol monomethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dioxolane, methylene chloride, chloroform , Trichloroethane, halogenated hydrocarbons such as tetrachloroethane, dimethylsulfoxide, other solvents such as propylene carbonate or mixtures thereof. In particular, methyl ethyl ketone and methyl isobutyl ketone are preferable.

Ink Ribbon In the present invention, the ink ribbon is for forming a decoration layer on a receiving layer of a transparent foil (a heat transfer foil in a state before the decoration layer is formed) using a thermal transfer printer. The ink ribbon used for manufacturing the thermal transfer foil has a base sheet, and at least a release layer and an ink layer in this order on one surface of the base sheet, and an adhesive layer and an antistatic layer on the ink layer. You may have further layers in this order. Moreover, what has further a heat-resistant slipping layer on the other surface of a base material sheet is good. According to a preferred embodiment, it is preferable to use an ink ribbon having a layer structure formed in the order of heat resistant slipping layer / base material sheet / peeling layer / ink layer / adhesive layer / antistatic layer. Further, according to another aspect, the ink ribbon has an ink layer and a single substrate sheet in which a metal vapor deposition layer in which a metal such as gold, silver, copper, zinc, and brass is deposited by vapor deposition is continuous. They may be provided in the surface order.

  FIG. 4 shows a schematic cross-sectional view of an example of an ink ribbon used for manufacturing the thermal transfer foil according to the present invention. The ink ribbon 410 shown in FIG. 4 is formed by laminating a release layer 430, an ink layer 440, an adhesive layer 450, and an antistatic layer 460 in this order on one surface of a base sheet 420. A heat resistant slipping layer 470 is formed on the other surface of the substrate sheet 420 (on the surface opposite to the ink layer 440). Hereinafter, each layer constituting the ink ribbon will be described. The adhesive layer and the antistatic layer can be formed in the same manner as the thermal transfer foil.

Base material sheet The material of the base material sheet constituting the ink ribbon used in the present invention can be a conventionally known material, and even if it is other than that, it has a certain degree of heat resistance and strength. If you have it, you can use it. For example, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, cellulose acetate, ionomer resin films, Examples thereof include paper such as condenser paper and paraffin paper, and non-woven fabric. These may be used alone, or a laminate in which these are arbitrarily combined may be used. Among these, polyethylene terephthalate which is a versatile plastic that can be thinned and is inexpensive is preferable.

  Although the thickness of a base material sheet can be suitably selected according to material so that intensity | strength, heat resistance, etc. may become suitable, Usually, about 1-20 micrometers is preferable, More preferably, it is 3-10 micrometers.

  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 (primer process).

Ink Layer The ink layer constituting the ink ribbon used in the present invention may be any one that contains a resin and a colorant, and various known ink layers can be used. In the present invention, the decorative layer can be formed by transferring the ink layer onto the receiving layer of the transparent foil by a thermal transfer printer using an ink ribbon having an ink layer.

  Examples of the resin used for the ink layer include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, polyvinyl acetate resin, and vinyl chloride-vinyl acetate. Polymer resin (vinyl acetate resin), polyvinyl butyral resin, polyvinyl acetal resin, vinyl resins such as polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins Examples thereof include resins and polyester resins. In the present invention, these resins may be used alone or in combination of two or more. Among these, from the viewpoints of heat resistance, colorant migration, and the like, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable, and a mixed resin of an acrylic resin and a vinyl acetate-based resin is preferable. Particularly preferred.

  As the colorant used in the ink layer, conventionally known colorants can be used, but those having good characteristics as a printing material, for example, a sufficient color density, and change depending on light, heat, temperature, etc. Those that do not fade are preferred. The colorant preferably exhibits at least one color selected from the group consisting of black, white, silver, cyan, magenta, yellow, red, green, and blue. For example, as a colorant, carbon black for black, titanium oxide for white, and inorganic materials such as aluminum for silver, C.I. for cyan, magenta, yellow, red, green, and blue. I. It is preferable to use each pigment described in Pigment.

  The ink layer is prepared by dissolving or dispersing the above-mentioned resins and colorants with the necessary additives in an appropriate solvent. Gravure coating, roll coating, comma coating, gravure printing It can be formed by applying and drying by a known means such as a method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the ink layer is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.5 to 3.0 μm.

Heat-resistant slip layer The heat-resistant slip layer constituting the ink ribbon used in the present invention is provided on the surface of the base sheet opposite to the ink layer, and is used for sticking and wrinkling due to the heat of the thermal head of the thermal transfer printer. This is to prevent adverse effects such as. The heat resistant slipping layer is mainly composed of a heat resistant resin. Examples of the heat resistant resin include 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, and chlorinated polyol Fin resins.

  In addition, the heat-resistant slipping layer is prepared by dissolving or dispersing the above heat-resistant resin with a necessary additive in an appropriate solvent, gravure coating method, roll coating method, comma coating method, It can be formed by applying and drying by a known means such as a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Examples of the additive include a slipperiness imparting agent, a crosslinking agent, a release agent, an organic powder, and an inorganic powder. Examples of the slipperiness-imparting agent include phosphate ester, silicone oil, graphite powder, silicone-based graft polymer, fluorine-based graft polymer, acrylic silicone graft polymer, polyacrylsiloxane, and polyarylsiloxane.

  Furthermore, the heat resistant slipping layer is prepared by dissolving or dispersing an ink obtained by adding a necessary additive such as a slipperiness imparting agent to the above resin in an appropriate solvent, using a gravure coating method, a roll coating method, a comma It can be formed by applying and drying by known means such as a coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Usually, the thickness of the heat-resistant slipping layer is preferably in the range of 0.05 to 3.0 μm, and more preferably in the range of 0.1 to 1.0 μm.

Release Layer The release layer that constitutes the ink ribbon used in the present invention is a layer that is provided so that the ink layer can be easily released from the base sheet during thermal transfer. Further, after the transfer from the ink ribbon to the heat transparent foil by thermal transfer to form the heat transfer foil, the decorative layer of the heat transfer foil is protected. Moreover, when manufacturing a decorative molded product, it plays the role which adheres to the surface of a resin molding. In the present invention, the release layer contains a resin and may further contain an additive and the like. The resin used for forming the release layer is preferably formed using a thermoplastic resin. Examples include acrylic resins, polyester resins, cellulose derivative resins, polyvinyl acetal resins, polyvinyl butyral resins, vinyl chloride-vinyl acetate copolymers, and chlorinated polyolefin resins.

  Furthermore, the release layer is prepared by dissolving or dispersing the above-mentioned resin with the necessary additives in an appropriate solvent. The gravure coating method, roll coating method, comma coating method, gravure printing method, screen It can be formed by applying and drying by known means such as a printing method and a gravure reverse roll coating method. Usually, the thickness of the adhesive layer is preferably in the range of 0.05 to 3.0 μm, and more preferably in the range of 0.1 to 1.0 μm.

Manufacturing method of thermal transfer foil The manufacturing method of the thermal transfer foil according to the present invention includes the following steps (1) to (3):
(1) A step of preparing a transparent foil having a base material and a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in this order on one surface of the base material;
(2) preparing a base sheet and an ink ribbon having a release layer and an ink layer in this order on one surface of the base sheet;
(3) A step of forming a pattern layer on the receptor layer on the receptor layer of the transparent foil by a thermal transfer printer using the ink ribbon, and subsequently forming a color material layer on the pattern layer The color material layer is formed so as to cover the pattern portion of the pattern layer and the peripheral portion of the color material layer is not in contact with the peripheral portion of the region to be thermally transferred to the transfer target. A process. By forming the color material layer of the thermal transfer foil by such a manufacturing process, the peripheral portion of the color material layer after the thermal transfer is not exposed to the outside, and the durability of the decorative layer of the decorative molded product can be improved. it can.

  In addition, in this invention, transparent foil is a transfer foil in the state before forming a decoration layer. FIG. 5 shows a schematic cross-sectional view of an example of a transparent foil used for producing the thermal transfer foil according to the present invention. A transparent foil 310 shown in FIG. 5 is formed by laminating a release layer 130, a hard coat layer 140, an anchor coat layer 150, and a receiving layer 160 in this order on one surface of a substrate 120. The antistatic layer 210 is formed on the surface of the substrate 120 opposite to the receiving layer 160. In addition, about the structure of each layer which forms transparent foil, it is as having demonstrated with the structure of each layer of said heat transfer foil.

Manufacturing method of decorative molded product having a decorative layer The decorative molded product according to the present invention is preferably formed by the above-mentioned injection molding simultaneous transfer decorative method using the above-mentioned thermal transfer foil. According to a preferred embodiment, the method for producing a decorative molded product includes the following steps (4) to (7):
(4) preparing a thermal transfer foil manufactured by the above thermal transfer foil manufacturing method;
(5) inserting the thermal transfer foil into an in-mold mold,
(6) a step of injecting and injecting molten injection resin into the mold;
(7) The step of integrating the thermal transfer foil and the injection resin to form a decorative layer on the surface of the resin molded body is included. Furthermore, after the resin molded body is cooled and taken out from the mold, a decorative molded product can be obtained by peeling the release sheet of the transfer foil. By manufacturing a decorative molded product by such a manufacturing process, a complicated design such as gradation can be expressed on the surface of the resin molded body.

Moreover, according to another aspect, the manufacturing method of a decorative molded product includes the following steps (8) to (10):
(8) a step of preparing a thermal transfer foil manufactured by the above method of manufacturing a thermal transfer foil;
(9) contacting the thermal transfer foil on the molded resin body;
(10) a step of performing roll transfer by thermal pressure while abutting,
May be included. Furthermore, a decorative molded product can be obtained by peeling the release sheet of the transfer foil. By manufacturing a decorative molded product by such a manufacturing process, a complicated design such as gradation can be expressed on the surface of the resin molded body.

  The injection resin used when producing a decorative molded product by injection molding such as in-mold molding or insert molding may be a thermoplastic resin or thermosetting resin (including two-component curable resin) that can be injection molded. Various known resins can be used. Examples of such thermoplastic resins include polystyrene resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin. Examples of the thermosetting resin include a two-component curable urethane resin and an epoxy resin. In the present invention, these resins may be used alone or in combination of two or more.

  A conventionally known molded resin body can be used as the molded resin body used when producing a decorative molded product by roll transfer. For example, a resin body molded from the above thermoplastic resin can be used.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not construed as being limited to the contents of the following examples.

Example 1
Preparation of transparent foil First, as a base material, a 50 μm thick PET film (trade name: F99, manufactured by Toray Industries, Inc.) was prepared. A release layer having a thickness of 2 μm was formed on one surface of the substrate by a gravure reverse coating method using a release layer ink having the following composition. Next, a hard coat layer having a thickness of 5 μm was formed on the release layer by a gravure reverse coat method using a hard coat layer ink having the following composition. Then, the hard coat layer was irradiated with ultraviolet rays from a mercury soot and crosslinked and cured to such an extent that unreacted acrylate (acryloyl) groups remained.
Composition of release layer ink / Melamine resin-based release agent (manufactured by Dainichi Seika Co., Ltd., trade name: EX-114D medium):
100 parts by mass / curing agent (manufactured by Dainichi Seika Co., Ltd., trade name: PTC NO. 7 curing agent): 10 parts by mass
Composition of hard coat layer ink / UV curable resin (component: urethane acrylate prepolymer, manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam EXF-HT-S) 60 parts by mass / reactive inorganic particles (reactive colloidal Silica particles, average particle diameter d50: 44 nm, manufactured by Nissan Chemical Industries, Ltd., trade name: MIBK-SD-L 40 parts by mass, polyfunctional isocyanate-based curing agent (component: hexanemethylene diisocyanate, Dainichi Seika Co., Ltd.) Product name: PTC-RC3 curing agent): 10 parts by mass

Subsequently, an anchor coat layer having a thickness of 3 μm was formed on the hard coat layer by a gravure reverse coat method using an ink for an anchor coat layer having the following composition. Further, a receiving layer having a thickness of 1 μm was formed on the anchor coat layer by a gravure reverse coating method using a receiving layer ink having the following composition. Further, an antistatic layer having a thickness of 0.1 μm was formed on the other surface of the substrate by a gravure reverse coating method using an antistatic layer ink having the following composition. Thus, a transparent foil 1 having a layer structure formed in the order of antistatic layer / base material / release layer / hard coat layer / anchor coat layer / receiving layer was produced.
Composition of ink for anchor coat layer / Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC):
70 parts by mass / polyfunctional isocyanate curing agent (component: hexanemethylene diisocyanate, manufactured by Dainichi Seika Co., Ltd., trade name: PTC-RC3 curing agent): 30 parts by mass
Composition of ink for receiving layer: Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC):
80 parts by mass, vinyl chloride vinyl acetate copolymer (DNP Fine Chemical Co., Ltd., trade name: SA Varnish)
20 parts by mass
Composition of antistatic layer ink / conductive polymer (manufactured by Nagase ChemteX Corporation, trade name: Denatron) 20 parts by mass / pure water (manufactured by Wako Pure Chemical Industries, Ltd., trade name: pure water) 30 parts by mass The above antistatic layer ink was appropriately diluted with water, and each ink except the antistatic layer ink was appropriately diluted with an organic solvent.

Preparation of Ink Ribbon First, mixed resin and colorant were dissolved in an organic solvent with the following composition to prepare ink for ink layer 1 and ink for ink layer 2. Next, a release layer having a thickness of 0.3 μm was formed on one surface of a PET base sheet having a thickness of 4.5 μm by a gravure reverse coating method using a release layer ink having the following composition. Subsequently, the ink layer 1 and the ink layer 2 having a thickness of 0.5 μm are sequentially formed on the release layer by the gravure reverse coating method using the ink for the ink layer 1 and the ink for the ink layer 2 described above. Formed. Then, an adhesive layer having a thickness of 0.3 μm was formed on the ink layer by the gravure reverse coating method using the adhesive layer ink. As described above, an ink ribbon having a layer structure formed in the order of the base sheet / release layer / ink layer / adhesive layer was produced.
Composition of ink for ink layer 1 (extracted pattern layer) Color ink material (DNP fine chemical) in which 40 parts by mass of black colorant containing carbon black is mixed with 100 parts by mass of mixed resin of acrylic resin and vinyl acetate resin (CR700 series)
Composition of ink 1 for ink layer 2 (color material layer) Color ink material (DNP fine chemical) in which 40 parts by mass of silver-based colorant containing aluminum is mixed with 100 parts by mass of mixed resin of acrylic resin and vinyl acetate resin (CR700 series)
Composition of release layer ink (ink ribbon) mixed resin of acrylic resin and vinyl acetate resin (DNP Fine Chemical Co., Ltd., release varnish DX): 100 parts by mass
Composition of ink for adhesive layer / Acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., BR83): 100 parts by mass

Production of Thermal Transfer Foil Using the thermal transfer printer equipped with a thermal head on the receiving layer of the transparent foil 1 produced above and the ink ribbon produced above, a patterned layer (see FIG. 2) is formed on the receiving layer of the transparent transfer foil. 10), covering the pattern portion (11 in FIG. 2) of the pattern layer on the pattern layer, and the peripheral portion (30 in FIG. 2) of the color material layer is thermally transferred to the transfer object. A color material layer (20 in FIG. 2) was formed so as not to contact the peripheral portion (50 in FIG. 2) of the region (40 in FIG. 2: inner portion of the dotted line). Thus, a thermal transfer foil 1 having a layer structure formed in the order of antistatic layer / base material / release layer / hard coat layer / anchor coat layer / receptor layer / extracted layer / adhesive layer was produced. The adhesive layer formed on the color material layer of the thermal transfer foil 1 is obtained by transferring the release layer of the ink ribbon.

Example 2
A thermal transfer foil 2 was produced in the same manner as in Example 1 except that the composition of the ink for the ink layer 2 was changed as follows.
Composition of ink 2 for ink layer 2 (color material layer) -40 parts by mass of a silver colorant containing a pigment having an average particle diameter of 2.0 µm in 100 parts by mass of a mixed resin of an acrylic resin and a vinyl acetate resin Mixed color ink material (DNP Fine Chemical Co., Ltd., CR700 series)

Comparative Example 1
A thermal transfer foil 3 was obtained in the same manner as in Example 1 except that a color material layer was formed on the entire surface of the punched pattern layer. The color material layer (20 in FIG. 1) of the thermal transfer foil 2 covers the pattern portion (11 in FIG. 1) of the pattern layer (10 in FIG. 1), and the peripheral portion (30 in FIG. 1) of the color material layer. Is formed beyond the peripheral portion (50 in FIG. 1) of the region (40 in FIG. 1: inner portion of the dotted line) to be thermally transferred to the thermal transfer member.

Comparative Example 2
A thermal transfer foil 4 was obtained in the same manner as in Example 2 except that a color material layer was formed on the entire surface of the punched pattern layer. The color material layer (20 in FIG. 1) of the thermal transfer foil 2 covers the pattern portion (11 in FIG. 1) of the pattern layer (10 in FIG. 1), and the peripheral portion (30 in FIG. 1) of the color material layer. Is formed beyond the peripheral portion (50 in FIG. 1) of the region (40 in FIG. 1: inner portion of the dotted line) to be thermally transferred to the thermal transfer member.

Performance evaluation of thermal transfer foil The thermal transfer foil produced above is inserted into an in-mold molding die, the molten resin is poured into the die (injection molding), in-mold molding is performed, and a decorative layer is provided. A decorative molded product was obtained. The durability of the decorative layer of the obtained decorative molded product was evaluated. The evaluation criteria are as follows.
Evaluation criteria 2: Excellent chemical resistance.
1: The chemical resistance was insufficient.

The results of the above evaluation are shown in Table 1. Each evaluation result shows that it is so favorable that a numerical value is large. It turns out that the heat transfer foil which satisfy | fills the structure of this invention can manufacture the decoration molded product which has a decoration layer excellent in durability compared with the heat transfer foil of a comparative example.

DESCRIPTION OF SYMBOLS 10 Extracted pattern layer 11 Extracted pattern part 20 Color material layer 30 The peripheral part of a color material layer 40 The area | region thermally transferred to a to-be-transferred body 50 The peripheral part of the area | region thermally transferred to a to-be-transferred body 110 Thermal transfer foil 120 Base material 130 Release layer 140 Hard Coat Layer 150 Anchor Coat Layer 160 Receiving Layer 170 Second Color Material Layer 180 First Color Material Layer 190 Color Material Layer 200 Adhesive Layer 210 Antistatic Layer 220 Transfer Layer 230 Release Sheet 310 Transparent Foil 410 Ink Ribbon 420 Base Material sheet 430 Release layer 440 Ink layer 450 Adhesive layer 460 Antistatic layer 470 Heat resistant slipping layer

Claims (13)

A heat transfer foil comprising a base material, and a punched pattern layer and a color material layer in this order on one surface of the base material,
The thermal transfer foil, wherein the color material layer covers a cut pattern portion of the cut pattern layer, and a peripheral portion of the color material layer does not contact a peripheral portion of a region to be thermally transferred to a transfer target.   The thermal transfer foil according to claim 1, wherein the color material layer comprises a color material that can be corroded by an acidic chemical and / or an alkaline chemical.   The thermal transfer foil according to claim 1, wherein the color material layer comprises a color material containing at least one selected from the group consisting of aluminum, chromium, gold, silver, and copper.   The thermal transfer foil according to any one of claims 1 to 3, wherein the color material layer comprises a pigment having an average particle diameter of 1.0 µm or more.   The thermal transfer foil according to any one of claims 1 to 4, wherein the punched pattern layer is black.   The thermal transfer foil comprises a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in order from the substrate side between the substrate and the punched pattern layer. The thermal transfer foil according to any one of 1 to 5. The hard coat layer comprises an ionizing radiation curable resin;
The anchor coat layer comprises a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
The thermal transfer foil according to claim 6, wherein the receiving layer comprises a thermoplastic resin.   The thermal transfer foil according to any one of claims 1 to 7, further comprising an adhesive layer on the color material layer.   The thermal transfer foil according to any one of claims 1 to 8, further comprising an antistatic layer on the other surface of the substrate.   The decorative molded product which has a to-be-transferred body and the decoration layer formed by transferring the thermal transfer foil as described in any one of Claims 1-9 on the to-be-transferred body. The following steps (1) to (3):
(1) A step of preparing a transparent foil having a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in this order on one surface of the substrate and the substrate;
(2) preparing a base sheet and an ink ribbon having a release layer and an ink layer in this order on one surface of the base sheet;
(3) A step of forming a pattern layer on the receptor layer on the receptor layer of the transparent foil by a thermal transfer printer using the ink ribbon, and subsequently forming a color material layer on the pattern layer The color material layer is formed so as to cover the pattern portion of the pattern layer and the peripheral portion of the color material layer is not in contact with the peripheral portion of the region to be thermally transferred to the transfer target. A process for producing a thermal transfer foil, comprising the steps of: The following steps (4) to (7):
(4) preparing a thermal transfer foil manufactured by the method for manufacturing a thermal transfer foil according to claim 11;
(5) inserting the thermal transfer foil into an in-mold mold,
(6) a step of injecting and injecting molten injection resin into the mold;
(7) A method for producing a decorative molded product, comprising the step of integrating the thermal transfer foil and the injection resin to form a decorative layer on the surface of the resin molded body. The following steps (8) to (10):
(8) preparing a thermal transfer foil manufactured by the method for manufacturing a thermal transfer foil according to claim 11;
(9) contacting the thermal transfer foil on the molded resin body;
(10) a step of performing roll transfer by thermal pressure while abutting,
A method for producing a decorative molded product, comprising: