JP5741995B2 - Transfer foil and manufacturing method thereof - Google Patents

Description

  The present invention relates to a transfer foil for in-mold molding having a release layer, a receiving layer, and a printing layer in this order on a base sheet, and a method for producing the same.

  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. In addition, there is a demand for moldability that can impart excellent surface properties such as high hardness and heat resistance to a decorative molded product and at the same time obtain a molded product with a more complicated shape.

  In order to solve the various problems as described above, when forming a printing layer by thermal transfer using an ink ribbon, the ink layer of the ink ribbon is mixed with an epoxy resin having a thermal softening temperature of 180 ° C. or more and a colorant. It has been proposed to use and form (for example, Patent Document 1). However, in this method, in the manufacturing process of the injection molding simultaneous transfer decoration method, the transfer foil has sufficient heat resistance and pressure resistance, particularly for the molten high-temperature resin injected and injected. I can't say that.

  Therefore, it is still desired to develop a transfer foil that has sufficient heat resistance and pressure resistance against the molten injection resin when the resin molded body is molded in-mold.

Japanese Patent No. 3793443

  The present invention has been made in view of the above-mentioned background art, and its purpose is to provide a transfer foil having sufficient heat resistance and pressure resistance against molten injection resin when a resin molded body is molded in-mold. It is in providing the manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have formed the receiving layer of the transfer foil for in-mold molding by using a resin material having a specific glass transition temperature, including an acrylic resin. The inventors have found that the problem can be solved and have completed the present invention.

That is, according to one aspect of the present invention,
A transfer foil for in-mold molding having a base sheet and at least a release layer, a receiving layer, and a print layer in this order on one surface of the base sheet,
The receiving layer is formed of a resin material containing an acrylic resin,
An in-mold transfer foil is provided in which the resin material has a glass transition temperature of 90 ° C. or higher.

According to another aspect of the present invention,
A method for producing a transfer foil for in-mold molding, comprising a base sheet, and at least a release layer, a receiving layer, and a print layer in this order on one surface of the base sheet,
(1) A step of preparing a transparent foil for in-mold molding having a base sheet and a release layer and a receiving layer in this order on one surface of the base sheet, the receiving layer comprising: Formed of a resin material containing an acrylic resin, and the resin material has a glass transition temperature of 90 ° C. or higher;
(2) a step of preparing an ink ribbon having at least a release layer and an ink layer in this order on one surface of the substrate and the substrate;
(3) A transfer foil for in-mold molding comprising a step of transferring the ink layer onto a receiving layer of the transparent foil for in-mold molding by a thermal transfer printer using the ink ribbon to form a printed layer. A manufacturing method is provided.

  The transfer foil for in-mold molding of the present invention has sufficient heat resistance and pressure resistance against molten injection resin when a resin molded body is molded in-mold. Thereby, distortion and flow of the printed image of the printed layer caused by heat and pressure applied to the transfer foil can be suppressed.

It is a schematic cross section which shows an example of the transfer foil for in-mold shaping | molding by this invention. It is a schematic cross section which shows an example of the ink ribbon used for manufacture of the transfer foil for in-mold shaping | molding by this invention. It is a schematic cross section which shows an example of the transparent night for in-mold shaping | molding used for manufacture of the transfer foil for in-mold shaping | molding by this invention.

Transfer foil for in-mold molding The transfer foil for in-mold molding of the present invention has at least a release layer, a receiving layer, and a printing layer in this order on one surface of the base sheet. A hard coat layer and an anchor layer may be further provided in this order between the release layer and the receiving layer, and an adhesive layer may be further provided on the printed layer. Moreover, you may further have an antistatic layer on the surface on the opposite side to the receiving layer of a base material sheet. According to one aspect of the present invention, in-mold molding has a layer structure formed in the order of antistatic layer / base sheet / release layer / hard coat layer / anchor layer / receptor layer / printing layer / adhesive layer. A transfer foil is provided.

  FIG. 1 shows a schematic cross-sectional view of an example of an in-mold transfer foil according to the present invention. The in-mold molding transfer foil 10 shown in FIG. 1 has a release layer 30, a hard coat layer 40, an anchor layer 50, a receiving layer 60, and a printing layer 70 on one surface of a substrate sheet 20. The adhesive layer 80 is laminated in this order, and the antistatic layer 90 is formed on the surface of the base sheet 20 opposite to the receiving layer 60. In the manufacturing process of the decorative molded product, the transferred transfer layer 100 includes a hard coat layer 40, an anchor layer 50, a receiving layer 60, a printed layer 70, and an adhesive layer 80, and is peeled off. The release sheet 110 includes an antistatic layer 90, a base sheet 20, and a release layer 30. Hereinafter, each layer constituting the transfer foil for in-mold molding will be described.

Base sheet In the present invention, the base sheet includes polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, and the like. Vinyl resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, acrylonitrile-butadiene-styrene Examples thereof include copolymer resins, cellulose triacetate, cellophane, polycarbonate, polyurethane resins and other elastomer resins. Among these, a polyester resin, particularly polyethylene terephthalate (PET) is preferable because of good moldability and releasability. Moreover, since the moldability, shape followability, and handleability are good, the thickness of the base sheet is preferably in the range of 25 μm to 150 μm, and more preferably in the range of 38 μm to 100 μm. .

Release layer The release layer in the present invention is provided so that a transfer layer comprising a hard coat layer, an anchor layer, a receiving layer, a printing layer, and an adhesive layer can be easily peeled off from the substrate sheet. Layer. By providing the release layer, the transfer layer can be reliably and easily transferred from the transfer foil for in-mold molding of the present invention to the transfer target, and a release sheet comprising an antistatic layer, a base material, and a release layer is formed. It can be reliably peeled off. 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, a melamine resin release agent and an acrylic resin release agent 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 transfer foil for in-mold molding to the resin molded product, and the molded product from wear, light, chemicals, etc. This is a layer for protecting the printing layer. According to a preferred embodiment, the hard coat layer is 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. In the present invention, ethylenically unsaturated groups such as vinyl group, (meth) acryloyl group, and allyl group are used. A functional group having a bond and an epoxy group.

  Examples of the polymer having an ionizing radiation-curable functional group include those obtained by polymerizing monomers such as acrylic (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate, those obtained by copolymerization of these monomers, polyester (meta ) Acrylate, and polymers such as polyether (meth) acrylate, and those obtained by polymerizing urethane (meth) acrylate are particularly preferable. In the present invention, these polymers may be used alone or in combination of two or more.

  Furthermore, the hard coat layer is an ink prepared by dissolving or dispersing the above-mentioned polymer with the necessary additives in an appropriate solvent, 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 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 layer The anchor layer in the present invention may be provided in order to improve the adhesion between the hard coat layer and the receiving layer. In the present invention, the anchor layer contains a resin and may further contain an additive or the like. The resin used for forming the anchor layer is a two-component curable urethane resin, a thermosetting urethane resin, a melamine resin, a cellulose ester resin, a chlorine-containing rubber resin, a vinyl chloride resin, an acrylic resin, an epoxy resin. Examples thereof include resins and vinyl copolymer resins.

  Furthermore, the anchor layer is prepared by dissolving or dispersing the above-mentioned resin with the necessary additives in an appropriate solvent, and using 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 anchor layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 1 to 5 μm.

Receiving Layer The receiving layer in the present invention is for forming and holding an ink layer transferred from the ink ribbon on the receiving layer during image formation by thermal transfer. In the present invention, the receptor layer is formed of a resin material containing an acrylic resin. In the present invention, the acrylic resin refers to a polymer of acrylic acid or methacrylic acid monomer or derivative thereof, a polymer of acrylic acid ester or methacrylic acid ester monomer or derivative thereof, acrylic acid or methacrylic acid monomer and other derivatives. It includes a copolymer with a monomer or a derivative thereof, and a copolymer of a monomer of an acrylate ester or a methacrylate ester with another monomer or a derivative thereof.

  According to a preferred embodiment of the present invention, the acrylic resin is preferably a copolymer of an acrylic ester or methacrylic ester monomer and another monomer or a derivative thereof. Examples of the acrylic acid ester or methacrylic acid ester monomer include alkyl acrylate and alkyl methacrylate, preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, lauryl acrylate, and lauryl methacrylate. Can be mentioned. Examples of other monomers include aromatic hydrocarbons, aryl group-containing compounds, amide group-containing compounds, and vinyl chloride, preferably styrene, benzylstyrene, phenoxyethyl methacrylate, acrylamide, and methacrylamide. it can. In the present invention, a copolymer of an alkyl acrylate or an alkyl methacrylate and at least one other monomer selected from the group consisting of an aromatic hydrocarbon, an aryl group-containing compound, and an amide group-containing compound, or a derivative thereof. It is particularly preferable to use it. By copolymerizing the monomers as described above, the concentration and releasability can be improved. Two or more acrylic resins may be mixed and used.

  In addition to acrylic resins, resin materials include vinyl chloride resins, vinyl chloride acrylic resins, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resins (vinyl acetate-based resins). Resin), halogenated polymers such as polyvinylidene chloride, vinyl polymers such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, ethylene and propylene, etc. It may further include at least one selected from the group consisting of copolymer resins of olefins and other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, and polycarbonate.

  In the present invention, the resin material forming the receptor layer has a glass transition temperature of 90 ° C. or higher, preferably 90 ° C. or higher and 130 ° C. or lower, more preferably 90 ° C. or higher and 105 ° C. or lower. In addition, when mixing and using 2 or more types of resin as a resin material, the glass transition temperature of the resin material after mixing should just be in the said range. When the glass transition temperature of the resin material is in the above range, the resin material has sufficient heat resistance and pressure resistance for the molten injection resin when in-mold molding.

  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.

Print layer The print layer in the present invention is formed by transferring the ink layer by a thermal transfer printer using an ink ribbon having an ink layer, and has a desired design on the surface when producing a decorative molded product. It imparts sex. By forming the print layer by thermal transfer in this way, it is possible to deal with the production 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. The print layer has the same components as the ink layer of the ink ribbon described below.

  Usually, the thickness of the printing layer is preferably in the range of 5 to 40 μm, and more preferably in the range of 5 to 30 μm. When the thickness of the printing 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 printed layer to the resin molded article 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 printing 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. And powder or fine flakes, 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 printing layer using a thermal transfer printer on a receiving layer of a transparent foil for in-mold molding (transfer foil in a state before the printing layer is formed). An ink ribbon used for producing a transfer foil for in-mold molding has at least a release layer and an ink layer in this order on one surface of a base material, and an adhesive layer and an antistatic layer on the ink layer. You may have further in order. Moreover, what has further a heat-resistant slipping layer on the other surface of a base material 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 / peeling layer / ink layer / adhesive layer / antistatic layer. According to another aspect, the ink ribbon has an ink layer and a metal deposition layer in which a metal such as gold, silver, copper, zinc, and brass is deposited by vapor deposition on a single base material. 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 an in-mold 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 220. A heat resistant slipping layer 270 is formed on the surface of the material 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 formation of the in-mold transfer foil.

The base material constituting the ink ribbon used in the present invention can be a conventionally known material, and even other materials have a certain degree of heat resistance and strength. Can be used. For example, polyethylene terephthalate, polyester, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, cellulose acetate, ionomer and other resin films, condenser paper, paraffin paper, and other non-woven fabrics Etc. 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 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 material may be surface-treated in order to improve the adhesiveness 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 material as the base material adhesion treatment. 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, a print layer can be formed by transferring an ink layer onto a receiving layer of a transparent foil for in-mold molding 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 slipping layer The heat-resistant slipping layer constituting the ink ribbon used in the present invention is provided on the surface of the substrate opposite to the ink layer, such as sticking or wrinkles due to the heat of the thermal head of the thermal transfer printer. This is to prevent the adverse effects of. 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 substrate during thermal transfer. In addition, after the ink ribbon is transferred from the ink ribbon to the in-mold molding transparent night by thermal transfer to form the in-mold molding transfer foil, the printed layer of the in-mold molding 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.

Production method of in-mold molding transfer foil The production method of the in-mold molding transfer foil of the present invention includes the following steps (1) to (3):
(1) A step of preparing a transparent foil for in-mold molding having a base sheet and a release layer and a receiving layer in this order on one surface of the base sheet, the receiving layer comprising: Formed of a resin material containing an acrylic resin, and the resin material has a glass transition temperature of 90 ° C. or higher;
(2) a step of preparing an ink ribbon having at least a release layer and an ink layer in this order on one surface of the substrate and the substrate;
(3) A step of transferring the ink layer onto the receiving layer of the transparent foil for in-mold molding by a thermal transfer printer using the ink ribbon to form a printed layer. By forming the printing layer of the transfer foil by such a manufacturing process, it is possible to omit the processes such as general plate making and printing necessary for other printing methods, and to reduce the cost by reducing the number of processes and equipment. it can.

  In addition, in this invention, the transparent foil for in-mold shaping | molding is a transfer foil in the state before forming a printing layer. FIG. 3 shows a schematic cross-sectional view of an example of a transparent night for in-mold molding used in the production of the transfer foil for in-mold molding according to the present invention. The transparent night 310 for in-mold molding shown in FIG. 3 has a release layer 30, a hard coat layer 40, an anchor layer 50, and a receiving layer 60 in this order on one surface of the base sheet 20. The antistatic layer 90 is formed on the surface opposite to the receiving layer 60 of the base sheet 20 by being laminated. In addition, about the structure of each layer which forms the transparent foil for in-mold shaping | molding, it is as having demonstrated with the structure of each layer of said transfer foil for in-mold shaping | molding.

Manufacturing method of resin molding (decoration molding) which has a decoration layer The resin molding (decoration molding article) which has a decoration layer of the present invention uses the above-mentioned transfer foil for in-mold molding, It is good to mold by injection molding simultaneous transfer decoration method. According to a preferred embodiment, the method for producing a decorative molded product includes the following steps (4) to (7):
(4) preparing a transfer foil for in-mold molding manufactured by the above-described method for manufacturing a transfer foil for in-mold molding;
(5) inserting the in-mold molding transfer foil into the in-mold molding die;
(6) a step of injecting and injecting molten injection resin into the mold;
(7) The step of integrating the in-mold molding transfer foil and the injection resin to form a decorative layer on the surface of the resin molded body. 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. In addition, the receiving layer of the transfer foil for in-mold molding is formed of a resin material containing an acrylic resin, and the resin material has a glass transition temperature of 90 ° C. or higher, so that it has excellent heat resistance and pressure resistance. It is possible to suppress distortion and flow of the image (design) of the decorative layer.

  The injection resin used in the manufacturing process of the decorative molded product may be any injection-moldable thermoplastic resin or thermosetting resin (including a two-component curable resin), and various known resins may be used. it can. 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.

  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
Production of transparent foil for in-mold molding First, a transparent biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was prepared as a substrate sheet. On one surface of the base sheet, a release layer ink having the following composition was applied by a gravure reverse coating method to form a release layer. Next, on the release layer, the hard coat layer ink having the following composition was applied with a thickness of 6 μm by a gravure reverse coat method 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: Melamine resin-based release agent (Daiichi Seika Co., Ltd., EX-114D medium): 100 parts by weight Curing agent (Daiichi Seika Co., Ltd., PTC No. 7 curing agent) ): 10 parts by weight
Composition of hard coat layer ink / UV curable resin (component: urethane acrylate prepolymer, manufactured by Dainichi Seika Co., Ltd., Seika Beam EXF-HT-S) 100 parts by weight

Subsequently, an anchor layer ink (two-component curable urethane resin) having the following composition was applied to the hard coat layer with a thickness of 3 μm by a gravure reverse coating method to form an anchor layer. Further, a receiving layer was formed on the anchor layer by applying a receiving layer ink having the following composition to a thickness of 0.7 μm by a gravure reverse coating method. In this way, the in-mold molding transparent foil 1 having a layer structure formed in the order of the base sheet / release layer / hard coat layer / anchor layer / receiving layer was produced.
Composition of ink for anchor layer: Acrylic polyol resin (manufactured by Dainichi Seika Co., Ltd., TM-VMAC): 100 parts by weight Polyisocyanate curing agent (component: hexanemethylene diisocyanate, Dainichi Seika Co., Ltd., PTC -RC3 curing agent): 15 parts by weight
Composition of receiving layer ink / acrylic resin (glass transition temperature: 100 ° C., manufactured by Dainichi Seika Co., Ltd., DNP-HS1):
100 parts by weight The above inks were 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 4.5 μm-thick PET base material 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 base material / peeling layer / ink layer / adhesive layer was produced.
Composition of ink for ink layer Color ink material (DNP Fine Chemical Co., Ltd., CR700 series) mixed with 100 parts by weight of a mixed resin of acrylic resin and vinyl chloride resin and 40 parts by weight of a colorant (below) )
Composition of release layer ink: Mixed resin of acrylic resin and vinyl acetate resin (DNP Fine Chemical Co., Ltd., release varnish DX): 100 parts by weight
Composition of ink for adhesive layer: Acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., BR83): 100 parts by weight

  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.

Production of transfer foil for in-mold molding On the receiving layer of transparent foil 1 for in-mold molding produced above, the ink layer of the ink ribbon was formed using the thermal transfer printer equipped with a thermal head and the ink ribbon produced above. The printed layer was formed by sequentially transferring. As described above, an in-mold transfer foil 1 having a layer structure formed in the order of the base sheet / release layer / hard coat layer / anchor layer / receptor layer / printing layer / adhesive layer was produced. The adhesive layer formed on the printed layer of the in-mold molding transfer foil 1 is a transfer of the ink ribbon release layer.

Example 2
90 ° C glass obtained by mixing an acrylic resin having a glass transition temperature of 100 ° C and an acrylic / vinyl acetate mixed resin having a glass transition temperature of 80 ° C as a resin material for forming the receiving layer A transfer foil 2 for printing was produced in the same manner as in Example 1 except that a receiving layer was formed by coating with a thickness of 0.5 μm using a mixed resin having a transition temperature.
Composition of Receptor Layer Ink 2 / Acrylic Resin (Glass Transition Temperature: 100 ° C., Dainichi Seika Co., Ltd., DNP-HS1):
90 parts by weight / acrylic / vinyl acetate mixed resin (glass transition temperature: 80 ° C., manufactured by Dainichi Seika Co., Ltd., TM-A1HS): 10 parts by weight

Example 3
As a resin material for forming the receptor layer, an acrylic resin having a glass transition temperature of 100 ° C. was used, and the receptor layer was formed by coating at a thickness of 5 μm. A transparent transfer foil 3 was produced.
Composition of Receptor Layer Ink 3 / Acrylic Resin (Glass Transition Temperature: 100 ° C., Dainichi Seika Co., Ltd., DNP-HS1):
100 parts by weight

Comparative Example 1
Example except that acrylic resin / vinyl chloride mixed resin having a glass transition temperature of 80 ° C. was used as the resin material for forming the receptor layer, and the receptor layer was formed by coating with a thickness of 0.5 μm. In the same manner as in Example 1, a transparent transfer foil 4 for printing was produced.
Composition of Ink 4 for Receiving Layer / Acrylic / Vinyl / Vinyl Mixed Mixed Resin (Glass Transition Temperature: 80 ° C., Dainichi Seika Co., Ltd. TM-A1HS)

Evaluation of heat resistance and pressure resistance The in-mold forming transfer foil 1 produced as described above is inserted into an in-mold mold, and the molten resin is poured into the mold (injection molding), and in-mold molding is performed. The resin molded product which has a decoration layer was obtained. The obtained molded body was observed for appearance such as the shape (unevenness) of the gate portion at the time of injection molding, distortion of the printed image on the surface of the molded body, flow, and the like. Similarly, the evaluation was performed using the in-mold forming transfer foils 2 to 4 produced above. The evaluation criteria are as follows.
Evaluation criteria : ○: There was no problem in appearance.
Δ: Slight but distortion of the printed image of the gate portion was observed.
X: The printed image of the gate portion disappeared, and the molding resin as the base was exposed.

The results of the above evaluation are shown in Table 1. It was found that the in-mold transfer foils produced in Examples 1 to 3 were superior in heat resistance and pressure resistance to the transfer foils produced in Comparative Example 1.

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

Claims (9)

A transfer foil for in-mold molding comprising a base sheet, and at least a release layer, a hard coat layer, an anchor layer, a receiving layer, and a printing layer in this order on one surface of the base sheet. Because
The hard coat layer is formed of a polymer having ionizing radiation-curable functional groups and has a thickness of 3 to 30 μm;
The anchor layer includes a urethane resin,
The receiving layer is formed of a resin material containing an acrylic resin and has a thickness of 0.05 to 1.0 μm;
A transfer foil for in-mold molding, wherein the resin material has a glass transition temperature of 90 ° C. or higher. The transfer foil for in-mold molding according to claim 1, wherein the print layer is formed by transferring the ink layer by a thermal transfer printer using an ink ribbon having an ink layer. The in-mold molding transfer foil, on said printing layer further comprises an adhesive layer, a transfer foil for in-mold according to claim 1 or 2. The colorant is black, white, silver, cyan, magenta, yellow, red, green, and exhibits at least one color selected from the group consisting of blue, according to any one of claims 1 to 3 Transfer foil for in-mold molding. A resin molded body produced by in-mold molding,
The resin molding which the said resin molding has a decoration layer decorated with the transfer foil for in-mold shaping | molding as described in any one of Claims 1-4 . A transfer foil for in-mold molding comprising a base sheet, and at least a release layer, a hard coat layer, an anchor layer, a receiving layer, and a printing layer in this order on one surface of the base sheet. The following steps (1) to (3):
(1) A transparent foil for in-mold molding having at least a release layer, a hard coat layer, an anchor layer, and a receiving layer in this order on a base sheet and one surface of the base sheet is prepared. The hard coat layer is formed of a polymer having an ionizing radiation-curable functional group and has a thickness of 3 to 30 μm, the anchor layer includes a urethane-based resin, and the receiving layer Is formed of a resin material containing an acrylic resin and has a thickness of 0.05 to 1.0 μm , and the resin material has a glass transition temperature of 90 ° C. or higher,
(2) a step of preparing an ink ribbon having at least a release layer and an ink layer in this order on one surface of the substrate and the substrate;
(3) A transfer foil for in-mold molding, including a step of transferring the ink layer onto a receiving layer of the transparent foil for in-mold molding by a thermal transfer printer using the ink ribbon to form a printed layer. Manufacturing method. The method for producing a transfer foil for in-mold molding according to claim 6 , wherein the transfer foil for in-mold molding further has an adhesive layer on the printed layer. The in-mold molding transfer according to claim 6 or 7 , wherein the colorant exhibits at least one color selected from the group consisting of black, white, silver, cyan, magenta, yellow, red, green, and blue. Foil manufacturing method. It is a manufacturing method of the resin molding which has a decoration layer, Comprising: The following process (4)-(7):
(4) a step of preparing an in-mold molding transfer foil produced by the method for producing an in-mold molding transfer foil according to any one of claims 6 to 8 ;
(5) inserting the in-mold molding transfer foil into the in-mold molding die;
(6) a step of injecting and injecting molten injection resin into the mold;
(7) A method for producing a resin molded body, comprising the step of integrating the in-mold molding transfer foil and the injection resin to form a decorative layer on the surface of the resin molded body.

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