JP5803625B2 - Thermal transfer foil and manufacturing method thereof - Google Patents

Description

  The present invention relates to a thermal transfer foil and a method for producing the same, and more specifically, a base material, a release layer, a hard coat layer, an anchor coat layer, and a receiving layer on one surface of the base material. The present invention relates to a thermal transfer foil and a manufacturing method thereof.

  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 method, the transfer layer side of the transfer foil for simultaneous injection molding decorating is arranged facing the inside of the mold and heated from the transfer layer side by a hot platen, and the transfer foil is placed inside the mold. Mold to conform to the 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.

  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. Further, there is a demand for moldability that can give a molded product with a more complicated shape while imparting excellent surface properties such as high hardness to the decorative molded product.

  Here, as a method for imparting excellent surface properties such as high hardness to the decorative molded product, an insert molding method for attaching a film, an in-mold hard coat molding method for transferring a hard coat layer by in-mold molding, a spray There are a method of forming a hard coat layer by painting, a screen printing method, and the like. In particular, the hard coat property of the coating is excellent. However, in the case of spray coating, there are problems that baking at a high temperature (for example, 150 ° C., 1 minute) or heating for a long time is required, and that ink loss is large and the cost is high.

  In addition, in order to impart surface properties such as high hardness to the decorative molded product, for example, a protective layer is formed using a protective layer material containing a polymer having a specific weight average molecular weight and a polyfunctional isocyanate. Has been proposed (see, for example, Patent Document 1). Furthermore, it has also been proposed to add colloidal silica to the protective layer material (see, for example, Patent Document 2).

  However, there is still a strong demand for the development of a thermal transfer foil that is excellent in the surface hardness of the decorative molded product, the three-dimensional shape followability, and the like.

Japanese Patent No. 3793443 JP 2009-137219 A

  As a result of studying the above-described background art, the present inventors, in particular, have a substrate, a release layer, a hard coat layer, an anchor coat layer, and a receptor layer on one surface of the substrate. In the thermal transfer foil having this order, when the hard coat layer is formed of a resin having excellent surface hardness and the receiving layer is formed of a resin having excellent ink receptivity, the adhesion between each layer of the thermal transfer foil is poor. I knew the problem.

  The present invention has been made in view of the above-mentioned background art and newly discovered problems, and its purpose is excellent in high hardness of the surface, three-dimensional shape followability, etc., and at the same time, a hard coat layer and an anchor coat layer, An object of the present invention is to provide a thermal transfer foil having improved adhesion between the anchor coat layer and the receiving layer and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by forming the hard coat layer, the anchor coat layer, and the receiving layer of the thermal transfer foil with a specific resin composition, respectively. As a result, the present invention has been completed.

That is, according to one aspect of the present invention,
A substrate and on one side of the substrate,
A release layer;
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 inorganic particle having a reactive functional group on the surface of the inorganic particle; Or a hard coat layer formed from an ink composition containing reactive irregularly shaped inorganic particles and a polyfunctional isocyanate, wherein the content of reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is A hard coat layer that is 13 to 60 mass based on the total mass of the polymer and reactive inorganic particles and / or reactive irregularly shaped inorganic particles;
An anchor coat layer comprising a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
There is provided a thermal transfer foil having a receiving layer containing a thermoplastic resin in this order.

  In the embodiment of the present invention, the inorganic particles are preferably silica particles.

  In the embodiment of the present invention, the thermoplastic resin contained in the receiving layer is preferably a vinyl chloride vinyl acetate copolymer.

  In the embodiment of the present invention, it is preferable that the anchor coat layer further includes a thermoplastic resin.

  In the aspect of the present invention, the anchor coat layer is composed of a resin obtained by reacting 50 to 80% by mass of an acrylic polyol and 10 to 30% by mass of a polyfunctional isocyanate, and a heat exceeding 0% by mass and 30% by mass or less. It preferably contains a plastic resin.

  In the embodiment of the present invention, it is preferable that the thermoplastic resin contained in the anchor coat layer is a vinyl chloride vinyl acetate copolymer.

  In the embodiment of the present invention, the polymer having the ionizing radiation curable functional group is an acrylic (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, or polyether (meth). It is preferably a polymer composed of at least one selected from acrylates.

  In the embodiment of the present invention, it is more preferable that the receiving layer further comprises an acrylic polyol.

  In the embodiment of the present invention, at least a part of the polyfunctional isocyanate of the anchor coat layer reacts with and / or adheres to at least a part of the acrylic polyol and / or the thermoplastic resin of the receiving layer. It is preferable to become.

  In the aspect of the present invention, it is preferable that a decorative layer is further provided on the receiving layer.

  In the aspect of the present invention, it is preferable that the decorative layer is formed by transferring the ink layer by a thermal transfer printer using an ink ribbon having the ink layer.

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

  In the aspect of the present invention, it is preferable to further have an antistatic layer on the other surface of the base material.

According to another aspect of the present invention,
A decorative molded product having a decorative layer decorated with the thermal transfer foil is provided.

According to another aspect of the present invention,
The following steps (1) to (3):
(1) On the base material and one surface of the base material,
A release layer;
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 inorganic particle having a reactive functional group on the surface of the inorganic particle; Or a hard coat layer formed from an ink composition containing reactive irregularly shaped inorganic particles and a polyfunctional isocyanate, wherein the content of reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is A hard coat layer that is 15 to 60 mass based on the total mass of the polymer and reactive inorganic particles and / or reactive irregularly shaped inorganic particles;
An anchor coat layer comprising a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
Preparing a transparent foil having a receiving layer comprising a thermoplastic resin in this order;
(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) There is provided a method for producing a thermal transfer foil, comprising a step of transferring the ink layer onto a receiving layer of the transparent foil by a thermal transfer printer using the ink ribbon to form a decorative layer. The

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:

  The thermal transfer foil of the present invention is excellent in high hardness of the surface, three-dimensional shape followability, etc. by forming the hard coat layer, the anchor coat layer, and the receiving layer with specific resin materials, respectively, and at the same time, The adhesion between the anchor coat layer, the anchor coat layer and the receiving layer can be improved.

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 of the present invention comprises at least a release layer, a hard coat layer, an anchor coat layer, and a receiving layer in this order on a substrate and one surface of the substrate. Is. According to a preferred embodiment, the decorative layer may be further provided on the receiving layer, and the adhesive layer may be further provided 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, there is provided a thermal transfer foil having a layer structure formed in the order of antistatic layer / base material / release layer / hard coat layer / anchor coat layer / receptive layer / decoration layer / adhesive layer. 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. 1 shows a schematic cross-sectional view of an example of a thermal transfer foil according to the present invention. A thermal transfer foil 10 shown in FIG. 1 has a release layer 30, a hard coat layer 40, an anchor coat layer 50, a receiving layer 60, a decoration layer 70, and an adhesive layer on one surface of a base material 20. 80 are laminated in this order, and the antistatic layer 90 is formed on the other surface (the side opposite to the receiving layer 60) of the substrate 20. In the manufacturing process of the decorative molded product, the transferred transfer layer 110 includes a hard coat layer 40, an anchor coat layer 50, a receiving layer 60, a decoration layer 70, and an adhesive layer 80, and is peeled off. The release sheet 120 includes an antistatic layer 90, a base material 20, and a release layer 30. Hereinafter, each layer constituting the thermal transfer foil will be described.

As the substrate in the substrate present invention, polyethylene, polyolefin resins such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, vinyl resins such as ethylene-vinyl alcohol copolymer , Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, acrylonitrile butadiene styrene Copolymers, 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.

Release layer The release layer in the present invention 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 In the present invention, the hard coat is 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 protects the molded product and the decorative layer from wear, light, chemicals, etc. It is a layer to do. 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 formed from an ink composition containing a functional inorganic particle and / or a reactive irregularly shaped inorganic particle 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. It should be noted that ionizing radiation curability is a material having an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, by being excited by irradiation with ultraviolet rays or electron beams to cause a polymerization reaction. It is the ability to crosslink and cure. The ionizing radiation curable functional group is a functional group capable of exhibiting the ionizing radiation curable property.

  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 (manufactured 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 the reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is 13 to 60% by mass, preferably 15 to 50% by mass, and more preferably 17 to 25% by mass. Here, the content of the reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is the amount of reactive inorganic particles and / or the total mass of the polymer and reactive inorganic particles and / or reactive irregularly shaped inorganic particles. It means the content of reactive irregularly shaped inorganic particles, and the polymer is a solid content. If the content of reactive inorganic particles and / or reactive irregularly shaped 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 in the present invention is a layer provided for improving the adhesion between the hard coat layer and the receiving layer. The anchor coat layer includes a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate, and may further include 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, chlorinated polyolefin resins, and the like. Polymers are preferred. 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 And / or at least a part of the thermoplastic resin reacts and / or adhesively adheres, and the adhesion between the anchor coat layer and the receiving layer can be improved. 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.

Receiving layer Since the receiving layer in the present invention cannot be directly printed on the anchor coat layer, it 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. The receiving layer contains a thermoplastic resin and may further contain an acrylic polyol. Examples of the thermoplastic resin include acrylic resins, polyester resins, cellulose derivative resins, polyvinyl acetal resins, polyvinyl butyral resins, vinyl chloride-vinyl acetate copolymers, chlorinated polyolefin resins, and the like. Polymers are preferred. When the anchor coat layer contains a thermoplastic resin, the adhesion between the anchor coat layer and the receiving layer can be further improved by using the same thermoplastic resin as the anchor coat.

  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.

Decoration layer The decoration layer in this invention is a layer provided in order to provide the designability of thermal transfer foil, and is a pattern layer expressing a pattern, a character, a pattern-like picture, etc. Examples of the pattern include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, stripe pattern and gradation pattern. In order to express a deeper design, for example, a layer order may be adopted such that a transparent anchor coat layer and / or a transparent medium layer is sandwiched between picture layers. 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.

  Examples of the resin for the ink used for forming the pattern 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 copolymer resin (vinyl acetate resin), polyvinyl butyral resin, polyvinyl acetal resin, vinyl resins such as polyvinylpyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane Examples thereof include 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.

  Colorants used in the above inks include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone yellow, hansa yellow A, quinacridone red, permanent Red 4R, organic pigments (including dyes) such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments made of metal powders such as aluminum and brass, titanium dioxide-coated mica, foil powders such as basic lead carbonate A pearl luster (pearl) pigment, a fluorescent pigment, or the like made of can be used alone or in combination of two or more.

  The handle 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 one in which a masking layer is further provided on the handle 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 (pattern 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 handle layer also functions 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 1-5 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.

Adhesive Layer The adhesive layer in the present invention is a layer for transferring the decorative layer to the resin molded body with good adhesiveness. In the present invention, the adhesive layer 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 in this invention is a layer formed in order to prevent the adhesion of the foreign material to transfer foil in the manufacturing process of a decorative molded product, especially a 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. 2 is 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 210 shown in FIG. 2 is formed by laminating a release layer 230, an ink layer 240, an adhesive layer 250, and an antistatic layer 260 in this order on one surface of a substrate sheet 220. A heat resistant slipping layer 270 is formed on the surface of the base sheet 220 opposite to the ink layer 240. 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 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 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 of the present invention includes the following steps (1) to (3):
(1) On the base material and one surface of the base material,
A release layer;
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 inorganic particle having a reactive functional group on the surface of the inorganic particle; Or a hard coat layer formed from an ink composition containing reactive irregularly shaped inorganic particles and a polyfunctional isocyanate, wherein the content of reactive inorganic particles and / or reactive irregularly shaped inorganic particles in the ink composition is A hard coat layer that is 15 to 60 mass based on the total mass of the polymer and reactive inorganic particles and / or reactive irregularly shaped inorganic particles;
An anchor coat layer comprising a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
Preparing a transparent foil having a receiving layer comprising a thermoplastic resin in this order;
(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 transferring the ink layer onto the receiving layer of the transparent foil by a thermal transfer printer using the ink ribbon to form a decoration layer. By forming the decorative layer of the thermal transfer foil by such a manufacturing process, it is possible to omit the steps of general plate making, printing plate, etc. necessary for other printing methods, and to reduce the cost by reducing the number of steps and equipment. it can.

  In addition, in this invention, transparent foil is a transfer foil in the state before forming a decoration layer. FIG. 3 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. 3 is formed by laminating a release layer 30, a hard coat layer 40, an anchor coat layer 50, and a receiving layer 60 in this order on one surface of a substrate 20. The antistatic layer 90 is formed on the surface of the substrate 20 opposite to the receiving layer 60. 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.

Method for producing a decorative molded product having a decorative layer The decorative molded product having a decorative layer according to the present invention is, for example, a transparent anchor layer between the pattern layers in order to express the thermal transfer foil, preferably a deeper design. Further, it is preferable to mold by the above-mentioned injection molding simultaneous transfer decorating method using a heat transfer foil that is devised such as a layer order sandwiching the transparent medium layer. 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):
The following steps (8) to (11):
(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, a 38 μm-thick PET film (trade name: F99, manufactured by Toray Industries, Inc.) was prepared as a substrate. A release layer was formed on one surface of the substrate by applying a release layer ink having the following composition at a coating amount of 1 g / m ² by a gravure reverse coating method. Subsequently, the hard coat layer ink having the following composition was applied on the release layer by a gravure reverse coating method at a coating amount of 12 g / m ² to form a hard coat layer. 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 1 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 ink 1 for hard coat layer / 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 size 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 Hardener): 10 parts by mass

Subsequently, an anchor coat layer was formed by applying an ink for anchor coat layer having the following composition on the hard coat layer by a gravure reverse coat method at a coating amount of 7 g / m ² . Further, on the anchor coat layer, a receiving layer ink having the following composition was applied at a coating amount of 3 g / m ² by a gravure reverse coating method to form a receiving layer. Further, an antistatic layer ink having the following composition was applied on the other surface of the substrate at a coating amount of 0.3 g / m ² to form an antistatic layer. 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 1 for Anchor Coat Layer / Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC): 60 parts by mass / polyfunctional isocyanate curing agent (component: hexanemethylene diisocyanate, Dainichi Seika) Product name: PTC-RC3 hardener): 25 parts by mass / vinyl chloride vinyl acetate copolymer (DNP Fine Chemicals, product name: SA Varnish)
15 parts by mass
Composition of Ink 1 for Receptor Layer • Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC): 80 parts by mass • Vinyl chloride vinyl acetate copolymer (manufactured by DNP Fine Chemical Co., Ltd., trade name) : SA varnish)
20 parts by mass
Composition of the antistatic layer ink 1 / 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, a mixed resin and a colorant were dissolved in an organic solvent with the following composition to prepare an ink for ink layer. 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, an ink layer having a thickness of 0.5 μm was formed on the release layer by the gravure reverse coating method using the above ink for ink layer. Then, an adhesive layer having a thickness of 0.3 μm was formed on the ink layer by a gravure reverse coating method using 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 Color ink material (DNP Fine Chemical Co., Ltd., CR700) obtained by mixing 40 parts by mass of any of the colorants (below) with 100 parts by mass of a mixed resin of acrylic resin and vinyl acetate resin series)
Composition of release layer ink (ink ribbon) 1 Mixed resin of acrylic resin and vinyl acetate resin (DNP Fine Chemical Co., Ltd., release varnish DX): 100 parts by mass
Composition of Ink 1 for Adhesive Layer / Acrylic Resin (Made by Mitsubishi Rayon Co., Ltd., BR83): 100 parts by mass

  As the colorant used in the ink for the ink layer, carbon black for black, titanium oxide for white, and inorganic materials such as aluminum for silver, cyan, magenta, yellow, red, green, and blue In C.I. I. Each pigment described in Pigment was used.

Preparation of thermal transfer foil On the receiving layer of the transparent foil 1 prepared above, the ink layer of the ink ribbon was sequentially transferred using the thermal transfer printer equipped with the thermal head and the ink ribbon prepared above, and the decoration layer was formed. Formed. Thus, the 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 / receptive layer / decoration layer / adhesive layer was produced. The adhesive layer formed on the decorative 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 hard coat layer ink was changed as follows.
Composition of hard coat layer ink 2 UV curable resin (component: urethane acrylate prepolymer, manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam EXF-HT-S) 70 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 30 parts by mass, polyfunctional isocyanate-based curing agent (component: hexanemethylene diisocyanate, Dainichi Seika Co., Ltd. Product name: PTC-RC3 Hardener): 10 parts by mass

Example 3
A thermal transfer foil 3 was produced in the same manner as in Example 1 except that the composition of the hard coat layer ink was changed as follows.
Composition of ink 3 for hard coat layer / UV curable resin (component: urethane acrylate prepolymer, manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam EXF-HT-S) 80 parts by mass / reactive inorganic particles (reactive Colloidal silica particles, average particle size d50: 44 nm, manufactured by Nissan Chemical Industries, Ltd., trade name: MIBK-SD-L 20 parts by mass, polyfunctional isocyanate-based curing agent (component: hexanemethylene diisocyanate, Dainichi Seika Co., Ltd. Product name: PTC-RC3 Hardener): 20 parts by mass

Example 4
A thermal transfer foil 4 was produced in the same manner as in Example 1 except that the composition of the ink for the receiving layer was as follows.
Composition of receiving layer ink 2 Vinyl chloride vinyl acetate copolymer (DNP Fine Chemical Co., Ltd., trade name: SA Varnish)
100 parts by mass

Example 5
A thermal transfer foil 5 was prepared in the same manner as in Example 2 except that the above-described receiving layer ink 2 was used as the receiving layer ink.

Example 6
A thermal transfer foil 6 was prepared in the same manner as in Example 3 except that the above-described receiving layer ink 2 was used as the receiving layer ink.

Example 7
A thermal transfer foil 7 was produced in the same manner as in Example 1 except that the composition of the anchor coat layer ink was changed as follows.
Composition of Ink 2 for Anchor Coat Layer / Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC): 75 parts by mass / polyfunctional isocyanate curing agent (component: hexanemethylene diisocyanate, Dainichi Seika) Product name: PTC-RC3 hardener): 15 parts by mass. Vinyl chloride vinyl acetate copolymer (DNP Fine Chemical Co., Ltd., product name: SA Varnish)
10 parts by mass

Example 8
A thermal transfer foil 8 was produced in the same manner as in Example 1 except that the composition of the anchor coat layer ink was changed as follows.
Composition of Ink 3 for Anchor Coat Layer / Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC): 60 parts by mass / polyfunctional isocyanate curing agent (component: hexanemethylene diisocyanate, Dainichi Seika) Product name: PTC-RC3 hardener): 20 parts by mass. Vinyl chloride vinyl acetate copolymer (DNP Fine Chemical Co., Ltd., product name: SA Varnish)
20 parts by mass

Example 9
A thermal transfer foil 9 was produced in the same manner as in Example 1 except that the composition of the anchor coat layer ink was changed as follows.
Composition of Ink 4 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, Dainichi Seika) Product name: PTC-RC3 curing agent): 30 parts by mass

Comparative Example 1
A thermal transfer foil 10 was produced in the same manner as in Example 1 except that the composition of the hard coat layer ink was changed as follows.
Composition of hard coat layer ink 4 UV curable resin (component: urethane acrylate prepolymer, manufactured by Dainichi Seika Co., Ltd., trade name: Seika Beam EXF-HT-S) 100 parts by mass, polyfunctional isocyanate-based curing agent ( Component: Hexanemethylene diisocyanate, manufactured by Dainichi Seika Co., Ltd., trade name: PTC-RC3 curing agent): 20 parts by mass

Comparative Example 2
A thermal transfer foil 11 was produced in the same manner as in Example 1 except that the composition of the ink for the anchor coat layer was as follows.
Composition of Ink 5 for Anchor Coat Layer / Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., trade name: TM-VMAC): 75 parts by mass / vinyl chloride vinyl acetate copolymer (manufactured by DNP Fine Chemical Co., Ltd.) Name: SA Varnish)
20 parts by mass

Comparative Example 3
A thermal transfer foil 12 was produced in the same manner as in Example 1 except that the composition of the anchor coat layer ink was changed as follows.
Composition of anchor coat layer ink 6 Vinyl chloride vinyl acetate copolymer (DNP Fine Chemical Co., Ltd., trade name: SA Varnish)
100 parts by mass / polyfunctional isocyanate curing agent (component: hexanemethylene diisocyanate, manufactured by Dainichi Seika Co., Ltd., trade name: PTC-RC3 curing agent): 10 parts by mass

Performance Evaluation of Thermal Transfer Foil Each of the thermal transfer foils prepared above was evaluated for (1) surface hardness, (2) adhesion between layers, and (3) three-dimensional shape followability.

(1) Evaluation of surface hardness The heat transfer foil produced above was laminated on a micro slide glass (Preclin water edge polish, Matsunami Glass Industry Co., Ltd., trade name: S7213) using a roller. Thereafter, the pencil hardness was measured using a pencil scratch coating film hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., trade name: D-NP) and a pencil scratch test pencil (manufactured by Mitsubishi Pencil Co., Ltd.). .

(2) Evaluation of adhesion between each layer The heat transfer foil produced above was heat-sealed with an ABS resin plate with a heat sealer heated to 110 ° C. Then, it cut | disconnected to 15 mm width, it pulled at 50 mm / min using Tensilon (Orientec Co., Ltd. make, brand name: RTA-1T), and it was confirmed in which interface of each layer peeling | exfoliation occurred.
Evaluation criteria : ○: The adhesive layer of the thermal transfer foil and the ABS resin plate were peeled off, and the adhesiveness of the hard coat layer, anchor coat layer, and receptor layer was sufficient.
Δ: Some peeling occurred between the hard coat layer and the anchor coat layer, or between the anchor coat layer and the receiving layer, and the adhesion between the layers was not sufficient.
X: Peeling occurred between the hard coat layer and the anchor coat layer, or between the anchor coat layer and the receiving layer, and the adhesion between the layers was insufficient.

(3) Evaluation of three-dimensional shape followability The thermal transfer foil produced as described above is inserted into an in-mold molding die, the molten resin is poured into the die (injection molding), and in-mold molding is performed. A decorative molded product having a decorative layer was obtained. About the obtained molded product, the corner part appearance after injection molding and the appearance directly under the gate were observed. The evaluation criteria are as follows.
Evaluation criteria : ○: There was no problem in appearance.
-: Fine coating cracks and slight whitening were observed.
*: Remarkable paint cracking or whitening was observed.

The results of the above evaluation are shown in Table 1. The thermal transfer foil satisfying the composition of the present invention is superior in surface hardness, solid shape followability, and the like as compared with the thermal transfer foil of the comparative example, and at the same time, the hard coat layer and the anchor coat layer, the anchor coat layer and the receiving layer. It can be seen that the adhesion between each of the layers is excellent.

DESCRIPTION OF SYMBOLS 10 Thermal transfer foil 20 Base material 30 Release layer 40 Hard coat layer 50 Anchor coat layer 60 Receptive layer 70 Decoration layer 80 Adhesive layer 90 Antistatic layer 110 Transfer layer 120 Release sheet 210 Ink ribbon 220 Base sheet 230 Release layer 240 Ink layer 250 Adhesive layer 260 Antistatic layer 270 Heat-resistant slip layer 310 Transparent foil

Claims (16)

On the substrate and one side of the substrate,
A release layer,
Vinyl group as the ionizing radiation-curable functional group, (meth) acryloyl group, a polymer having at least one selected from an allyl group and an epoxy group, a vinyl group on the surface of the inorganic particles, (meth) acryloyl group and an allyl group, A hard coat layer formed from an ink composition comprising a reactive inorganic particle and / or a reactive irregularly shaped inorganic particle having a reactive functional group selected from polyfunctional isocyanate and a reaction in the ink composition A hard coat layer in which the content of the reactive inorganic particles and / or reactive irregularly shaped inorganic particles is 13 to 60 % by mass with respect to the total mass of the polymer and the reactive inorganic particles and / or reactive irregularly shaped inorganic particles;
An anchor coat layer comprising a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
A receiving layer comprising a thermoplastic resin;
A decorative layer,
A thermal transfer foil comprising:   The thermal transfer foil according to claim 1, wherein the inorganic particles are silica particles.   The thermal transfer foil according to claim 1 or 2, wherein the thermoplastic resin contained in the receiving layer is a vinyl chloride vinyl acetate copolymer.   The thermal transfer foil according to claim 1, wherein the anchor coat layer further comprises a thermoplastic resin.   The anchor coat layer comprises a resin obtained by reacting 50 to 80% by mass of an acrylic polyol and 10 to 30% by mass of a polyfunctional isocyanate, and a thermoplastic resin exceeding 0% by mass and 30% by mass or less. The thermal transfer foil according to claim 4.   The thermal transfer foil according to claim 4 or 5, wherein the thermoplastic resin contained in the anchor coat layer is a vinyl chloride vinyl acetate copolymer.   The polymer having an ionizing radiation-curable functional group is at least one selected from acrylic (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate. The thermal transfer foil according to any one of claims 1 to 6, which is a polymer.   The thermal transfer foil according to claim 1, wherein the receiving layer further comprises an acrylic polyol.   The thermal transfer according to claim 8, wherein at least a part of the polyfunctional isocyanate of the anchor coat layer is reacted and / or adhesively bonded with at least a part of the acrylic polyol and / or the thermoplastic resin of the receiving layer. Foil. The thermal transfer foil according to any one of claims 1 to 9, wherein the decorative layer is formed by transferring the ink layer by a thermal transfer printer using an ink ribbon having an ink layer. The thermal transfer foil according to any one of claims 1 to 10 , further comprising an adhesive layer on the decorative layer. The thermal transfer foil according to any one of claims 1 to 11 , further comprising an antistatic layer on the other surface of the substrate. Claim 1 comprising a decorative layer which is decorated by thermal transfer foil according to any one of 12, the decorative molded article. The following steps (1) to (3):
(1) On the base material and one surface of the base material,
A release layer;
Vinyl group as the ionizing radiation-curable functional group, (meth) acryloyl group, a polymer having at least one selected from an allyl group and an epoxy group, a vinyl group on the surface of the inorganic particles, (meth) acryloyl group and an allyl group, A hard coat layer formed from an ink composition comprising a reactive inorganic particle and / or a reactive irregularly shaped inorganic particle having a reactive functional group selected from polyfunctional isocyanate and a reaction in the ink composition A hard coat layer in which the content of the reactive inorganic particles and / or reactive irregularly shaped inorganic particles is 13 to 60 % by mass with respect to the total mass of the polymer and the reactive inorganic particles and / or reactive irregularly shaped inorganic particles;
An anchor coat layer comprising a resin obtained by reacting an acrylic polyol and a polyfunctional isocyanate;
Preparing a transparent foil having a receiving layer comprising a thermoplastic resin in this order;
(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 method for producing a thermal transfer foil, comprising a step of transferring the ink layer onto a receiving layer of the transparent foil by a thermal transfer printer using the ink ribbon to form a decorative layer. The following steps (4) to (7):
(4) a step of preparing a thermal transfer foil manufactured by the method of manufacturing a thermal transfer foil according to claim 14 ;
(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 14 ;
(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:

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