JP2017065234A - Thermal transfer recording medium used in thermal transfer decorative method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve a problem that metallic sheen generated during second and third thermal transfers appears dirty in a thermal transfer decorative method for obtaining a thermal transfer record having colored metallic sheen when seen from an opposite surface on a side in which an image receiving material is transferred, by performing transfer superposition using three kinds of thermal transfer recording media having a colored layer, a deposition layer, and a black hiding layer on a transparent image receiving material.SOLUTION: In the thermal transfer decorative method, as a first thermal transfer recording medium having the colored layer, a thermal transfer recording medium obtained by disposing at least a heat-resistant peel layer and a colorant containing adhesive layer in this order is used.SELECTED DRAWING: None

Description

The present invention relates to a thermal transfer recording medium used in a thermal transfer decoration method for obtaining a thermal transfer recording material having a metallic luster colored when viewed from the opposite side of the side thermally transferred to a transparent image receptor such as glass.

Conventionally, as a method for obtaining an image having a colored metallic luster using a thermal transfer recording apparatus, for example, there is a method introduced in Patent Document 1. According to this, first, an image is first transferred with a thermal transfer recording medium provided with a metal vapor deposition layer, and then the image is overlaid and transferred with a thermal transfer recording medium provided with a colored layer, thereby obtaining an image having a colored metallic luster. ing.

In recent years, in devices consisting of flat displays such as smartphones and tablet terminals, all images are imaged using a thermal transfer recording medium in order to display the manufacturer's logo, model name, etc. with a metallic luster when viewed from the display surface. There is a potential need to transcribe.

This method has the following advantages. That is, 1. When a thermal transfer recording apparatus using a thermal head is used as an apparatus for transferring an image, an image pattern can be set freely, which is advantageous for producing a small number of copies.
2. By separating the thermal transfer recording medium provided with the colored layer and the thermal transfer recording medium provided with the metallic gloss layer, the degree of freedom in image design is increased. For example, it is possible to easily obtain an image such that the manufacturer logo is gold and the model name is silver.
3. By making the side on which the transfer of the transparent image receptor has not been performed the front side of the device, the image having the metallic luster becomes the inside of the device as compared with the method described in Patent Document 1, and the image is stained or damaged. You can keep the beauty for a long time.

From the viewpoint of obtaining the above merits, the present inventor examined the following thermal transfer decoration method using a conventionally known thermal transfer recording medium.
1) An image is transferred to a transparent image receptor such as glass using a first thermal transfer recording medium in which at least a colored layer is provided on a substrate.
2) The image is overlaid and transferred using the second thermal transfer recording medium in which at least a release layer, a metal vapor deposition layer, and an adhesive layer are provided in this order on the substrate.
3) Further, the image is transferred onto the image with a third thermal transfer recording medium in which at least a black masking layer is provided on the substrate. In some cases, the image is further transferred onto another thermal transfer recording medium. This is because when the transparent image receptor is viewed from the surface opposite to the surface on which the transfer has been performed, light passes through the images formed on the first and second thermal transfer recording media. In order to prevent the metallic luster from becoming weak, the transfer is performed by superimposing the second thermal transfer recording medium on the second thermal transfer recording medium.
4) A colored metallic gloss image is obtained by viewing the transparent image receptor from the surface opposite to the surface on which the transfer has been performed.

However, as the first thermal transfer recording medium, a conventionally known thermal transfer recording medium in which a heat-resistant slipping layer is provided on one side of the substrate and a colorant-containing adhesive layer as a colored layer is provided on the other side is used. In this case, coloring is performed when the second thermal transfer recording medium is used for overtransfer from the image onto which the coloring material-containing adhesive layer as the colored layer is transferred, or when the third thermal transfer recording medium is further transferred from there. The surface of the colorant-containing adhesive layer as a layer was damaged by the heat during the repeated transfer, resulting in a fine uneven state, resulting in a problem that the metallic luster appeared dull.

On the other hand, in the system disclosed in Patent Document 1, first, a thermal transfer layer in which a heat-resistant slipping layer is provided on one surface of a substrate and a release layer, an anchor layer, a metal vapor deposition layer, and an adhesive layer are provided in this order on the other surface. An image is formed by thermal transfer using a recording medium, and then an image is formed by thermal transfer using a thermal transfer recording medium having a colored layer. That is, since an image that is easily melted by heat is formed on an image having a hard base, unlike the present decoration method, a problem that the metallic luster appears dull in the final image hardly occurs.

However, in the method in Patent Document 1, first, an image having a metallic gloss is transferred to an image receiver, and a colored layer is transferred from the image to the image receiving body. . For this reason, a colored metallic gloss image cannot be obtained by the method of transferring to a transparent image receptor and viewing from the opposite side. When viewed from the transfer side, a colored metallic gloss image can be obtained. Is not obtained, and it is difficult to maintain the beauty of the transcript for a long time.

Therefore, as a result of earnest research, the present inventor has found that the first thermal transfer recording medium is a heat-resistant slipping layer on one side of the substrate, and at least a heat-resistant release layer and a colorant-containing adhesive layer on the other side. By using the thermal transfer recording medium provided with the above in this order, it was found that the phenomenon of dull metallic luster can be eliminated even in the thermal transfer decoration method of the present invention, and the present invention was completed.

JP-A-9-39399

Thermal transfer using a first thermal transfer recording medium provided on a transparent image receptor such as glass with a heat-resistant slipping layer on one side of the substrate and a colorant-containing adhesive layer as at least a colored layer on the other side After the image is formed, a second heat transfer recording medium is used in which a heat-resistant slipping layer is provided on one surface of the substrate, and at least a release layer, a metal vapor deposition layer, and an adhesive layer are provided on the other surface in this order. An image is formed by thermal transfer, and further, thermal transfer is performed using a third thermal transfer recording medium on which a heat-resistant slipping layer is provided on one side of the substrate and at least a black masking layer is provided on the other side. A second thermal transfer recording medium in a thermal transfer decoration system that forms an image by superimposing and obtains a metallic glossy image when the transparent image receptor is viewed from the surface opposite to the surface to which the image is transferred. Even when an image is transferred on a third thermal transfer recording medium, the metallic luster is caused by heat. Not Kusuma damage, providing a first thermal transfer recording medium.

In the first invention, an image is formed by thermal transfer on a transparent image receptor using a first thermal transfer recording medium in which a heat-resistant slipping layer is provided on one side of a substrate and at least a colored layer is provided on the other side. Then, a heat-resistant slipping layer is formed on one surface of the substrate, and a second thermal transfer recording medium in which at least a release layer, a metal vapor deposition layer, and an adhesive layer are provided in this order on the other surface is overlaid by thermal transfer. Then, an image is formed by thermal transfer using a third thermal transfer recording medium on which a heat-resistant slipping layer is provided on one side of the substrate and at least a black masking layer is provided on the other side. In the thermal transfer decorating method, characterized in that the transparent image receptor is obtained by obtaining a thermal transfer recording material having a metallic luster colored when viewed from the surface opposite to the surface on which the transfer was performed, The first thermal transfer recording medium has at least a heat-resistant release layer and a color material on the other surface A thermal transfer recording medium, which is a thermal transfer recording medium formed by providing a sealable layer in this order.

In the second invention, the heat-resistant release layer of the first thermal transfer recording medium is composed of inorganic particles and a binder resin, and the content of the inorganic particles is 35% by weight to 80% by weight in the heat-resistant release layer. The thermal transfer recording medium according to the first aspect is characterized in that the heat-resistant release layer has a total light transmittance of 80% or more.

A third invention is the thermal transfer recording medium according to the second invention, wherein the inorganic particles are silica particles.

According to a fourth aspect of the invention, the surface of the heat-resistant release layer of the first thermal transfer recording medium is surface-treated with a colloidal silica sol solution, and the colorant-containing adhesive layer is provided thereon. A thermal transfer recording medium according to any one of the second and third inventions.

An image is formed by the first thermal transfer recording medium having the heat-resistant release layer and the colorant-containing adhesive layer of the present invention, and a second thermal transfer recording medium provided with a metal vapor deposition layer on the image, and further black concealment Even when an image is overlaid and transferred by thermal transfer on a third thermal transfer recording medium provided with a layer, the image surface of the first thermal transfer recording medium is not easily deformed by heat during transfer, and the phenomenon of dull metallic luster is eliminated. I was able to.

The first thermal transfer recording medium used in the decorating method of the present invention is provided with a heat-resistant slipping layer on one surface of a substrate and at least a heat-resistant release layer and a colorant-containing adhesive layer on the other surface in this order. The second thermal transfer recording medium is provided with a heat-resistant slipping layer on one surface of a substrate, and at least a release layer, a metal vapor deposition layer, and an adhesive layer in this order on the other surface. The third thermal transfer recording medium is a thermal transfer recording medium in which a heat-resistant slipping layer is provided on one surface of a substrate and at least a black concealing layer is provided on the other surface.
(Receiver)

Since the transparent receiver in the present invention is installed on the display surface in a device including a flat display such as a smartphone or a tablet terminal, visibility and durability are required. For this reason, it is suitable that it is transparent and hard. Moreover, it is preferable that the thickness of the device is as thin as possible. Specifically, a hard glass plate having a thickness of about 0.3 to 1.0 mm, a transparent hard plastic plate such as an acrylic resin or a polycarbonate resin, or the like is preferably used.
(Base material)

As a base material used in the first thermal transfer recording medium, the second thermal transfer recording medium, and the third thermal transfer recording medium of the present invention, a polyester film such as a polyethylene terephthalate film or a polyethylene naphthalate film, a polycarbonate film Polyamide film, aramid film, and other various plastic films generally used as a base film for this type of thermal transfer recording medium can be used. In addition, high density thin paper such as condenser paper can be used. The thickness of the substrate is usually about 1 to 10 μm, and in order to improve heat transfer, a range of 1 to 6 μm is preferable.
(Heat resistant slipping layer)

As the material of the heat-resistant slip layer used in the first thermal transfer recording medium, the second thermal transfer recording medium, and the third thermal transfer recording medium of the present invention, those conventionally used in thermal transfer recording media. Can be used without particular limitation, for example, heat-resistant resins such as silicone resins, fluororesins, epoxy resins, melamine resins, phenol resins, polyimide resins, nitrocellulose resins, and other resins modified with the above heat-resistant resins ( For example, a silicone-modified urethane resin, a silicone-modified acrylic resin, or the like may be used. From the viewpoints of heat resistance against thermal heads, lowering the dynamic friction coefficient at high temperatures, and cost. Particularly preferred are modified urethane resins, silicone-modified acrylic resins, or mixtures thereof.

Moreover, you may mix | blend a lubricant with the heat-resistant slipping layer of this invention. Examples of the lubricant include silicone oils (for example, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, fluorine-containing silicone oil, and epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, polyether-modified, etc. Various modified silicone oils), aspartate esters, fluorosurfactants, phosphate esters, paraffin waxes, higher fatty acid amides, esters and metal salts that exhibit lubricity in the liquid state It is done.

You may mix | blend other additives, such as an antistatic agent, with the heat-resistant slipping layer of this invention.

The heat-resistant slip layer of the present invention can be formed by coating and drying a coating solution obtained by dissolving and dispersing the above components in an appropriate solvent. The coating thickness of the heat-resistant slipping layer (coating thickness after drying, hereinafter the same) is suitably in the range of 0.05 to 0.8 μm from the viewpoint of achieving a good anti-sticking effect and preventing deterioration of heat conduction. It is. If the thickness of the heat resistant slipping layer is less than 0.05 μm, the heat resistance is insufficient and the heat of the thermal head causes a stick that sticks to the head during transfer, or the recording medium melts with the substrate due to heat and cannot be transferred. It may become. When the thickness exceeds 0.8 μm, heat conduction may deteriorate and transfer may be hindered.
(First thermal transfer recording medium)
(Coloring material-containing adhesive layer)

As the colorant-containing adhesive layer of the first thermal transfer recording medium of the present invention, a conventionally known thermal transfer ink layer comprising a heat-meltable or heat-softening vehicle and a colorant can be used without any particular limitation. As the vehicle, thermoplastic resins may be used alone or in combination of two or more. Moreover, you may use an additive suitably for a various objective.

Examples of the thermoplastic resin (including elastomer) include ethylene-vinyl acetate copolymer, ethylene-vinyl butyrate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer. Polymers, ethylene-acrylonitrile copolymers, ethylene acrylamide copolymers, ethylene copolymers such as ethylene-styrene copolymers, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl alcohol copolymers Vinyl chloride (co) polymers such as coalescence, (meth) acrylic acid ester resins, polyester resins, polyamide resins, epoxy resins, phenol resins, acetophenone-formaldehyde resins, cellulose resins, natural rubber, Styrene-butadiene copolymer, isoprene polymer, Ropuren polymers, petroleum resins, styrene resins, rosin resins, terpene resins, coumarone - indene resins, and thermoplastic polyurethane resins. These resins may be used alone or in combination of two or more.

Examples of the additive include a plasticizer, an antifoaming agent, a surfactant, and an antioxidant.

As the colorant, organic and inorganic color pigments and dyes generally used in the color layer of the thermal transfer recording medium can be used. In order to obtain a colored metallic glossy image, the colorant-containing color is used. Since the layer is required to have good light transmittance, a dye or an organic colored pigment is preferable. The content of the colorant in the colorant-containing colored layer is suitably 20 to 60% by weight.

The thickness of the colorant-containing adhesive layer is preferably in the range of 0.2 to 2.0 μm. When the thickness is less than 0.2 μm, it is difficult to obtain sufficient coloring power. If the thickness is greater than 2.0 μm, the transferability tends to be impaired.
(Heat-resistant release layer)

The heat-resistant release layer of the first thermal transfer recording medium is composed of inorganic particles and a binder resin.

Since the heat-resistant release layer of the first thermal transfer recording medium of the present invention requires not only heat resistance but also functional transparency, non-colorable metal oxide particles are preferred as the inorganic particles. As the metal oxide particles, silica, alumina, titanium oxide, zinc oxide, indium oxide, tin oxide, cerium oxide, niobium oxide and the like can be used, and the average particle size is 100 nm or less and the particle size is smaller. preferable. The total light transmittance as the heat-resistant release layer is preferably at least 80%.

As the coating liquid for the heat-resistant release layer comprising the metal oxide particles and the binder resin, the metal oxide particles can be dispersed in the solution using a dispersing device. From the viewpoint of the process, it is convenient to use the colloidal sol solution of the metal oxide particles. All of the colloidal sol solutions of metal oxide particles mentioned in the specific examples are commercially available. On the other hand, these metal oxide particle sol solutions are generally expensive except for silica and alumina. Accordingly, as the metal oxide particle sol solution used in the present invention, it is preferable to use a colloidal sol solution of silica or alumina from the viewpoint of cost. In addition, commercially available dispersion solvents for colloidal sol liquids are generally water-based. In the case of an aqueous system, a water-soluble resin or a dispersion type binder resin is selected as the binder resin described later. On the other hand, when the dispersion solvent of the colloidal sol liquid is an organic solvent, the binder resin can be used in a dissolved state, and thus there is an advantage that the selection range of the resin is widened. As the metal oxide particles used in the present invention, it is more preferable to use silica particles in which not only the aqueous colloid sol but also colloidal organosols of various organic solvents can be easily obtained from the viewpoint of cost and the above.

As described above, from the viewpoint of the transparency of the heat-resistant release layer, the smaller the particle size of the metal oxide particles, the better. Preferably, it is 50 nm or less, more preferably 30 nm or less. Further, from the viewpoint of solving the dullness problem of the thermal transfer decoration method of the present invention and the cutting property at the time of thermal transfer, the ratio of the metal oxide particles in the heat-resistant release layer is preferably as high as possible. However, from the functional aspect of the release layer as a thermal transfer recording medium, the heat-resistant release layer is required to satisfy both appropriate substrate adhesion and releasability from the substrate at the time of transfer and not to reduce the thermal sensitivity. . From the viewpoint of satisfying these, the content of the metal oxide particles is preferably 35% by weight to 80% by weight in the heat-resistant release layer. When the content is less than 35% by weight, the effect of eliminating the dull problem is low. In general, the higher the content of the metal oxide particles, the better the heat resistance and the cutting property at the time of transfer. However, when the content exceeds 80% by weight, the substrate adhesion of the heat resistant release layer decreases. As a result, the heat-resistant release layer is easily peeled off from the substrate, making it difficult to handle the thermal transfer recording medium.

As the binder resin, which is another component of the heat-resistant release layer, a conventionally known resin can be used. However, as described above, the heat-resistant release layer includes, as described above, the heat-resistant release layer and the substrate. A function that the adhesiveness is strong and the heat-resistant release layer has high peelability during thermal transfer is required. From this point of view, as binder resin, there are problems of acrylic resin with excellent heat resistance, hardness and transparency of the resin itself, and acrylic resin with poor adhesion between the heat-resistant release layer and the substrate during non-transfer. It is preferably composed of an adhesion-imparting agent resin for improving the point.

As an example of the acrylic resin, polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, and copolymers thereof are preferable. The weight average molecular weight Mw of the acrylic resin is preferably 500,000 or less. When Mw exceeds 500,000, the cohesive force of the resin increases, and it becomes difficult to cut during transfer, which may cause transfer failure.

As the adhesion-imparting agent resin, known resins having a softening point of 180 ° C. or lower can be used. For example, epoxy resins, alicyclic hydrocarbon resins, ketone resins, styrene resins, rosin resins, polyester resins, Coumarone-indene resin, phenol resin, modified resins thereof and the like are preferably used. In particular, a polyester resin, a ketone resin, or a mixture of a polyester resin and a ketone resin is preferable.

The thickness of the heat-resistant release layer is preferably 0.1 to 1.0 μm in a dry state. When the thickness is less than 0.1 μm, it is difficult to obtain a heat resistance effect. If the thickness exceeds 1.0 μm, the transfer sensitivity tends to decrease.

The content of the acrylic resin in the heat-resistant release layer solid content is 15% by weight to 60% by weight, and the content of the adhesion-imparting agent resin is 1% by weight to 30% by weight. It is preferable for achieving the problem of the heat-resistant release layer. More preferably, the content of the acrylic resin is in the range of 15% by weight to 45% by weight, and the content of the adhesion-imparting agent resin is in the range of 5% by weight to 20% by weight.

Further, for the purpose of further improving the heat resistance, the surface of the heat-resistant release layer is surface-treated with a colloidal metal oxide particle sol solution, and only the vicinity of the surface of the heat-resistant release layer is bonded to the metal oxide particles. Increasing the ratio relative to the adhesive resin improves the resolution of the dullness problem of the thermal transfer decorating method of the present invention, the appropriate substrate adhesion of the heat-resistant release layer, and the substrate during transfer. It is better in maintaining releasability from. The colloidal metal oxide particle sol solution for surface treatment may be an aqueous sol solution, but an organic solvent dispersion system is more preferred from the viewpoint of improving the wettability and adhesion of the coating solution to the heat-resistant release layer surface. Also from this viewpoint, the colloidal metal oxide particle sol liquid is more preferably a colloidal organosol liquid. Additives such as resins and silane coupling agents may be added to the coating liquid composed of the colloidal metal oxide particle sol liquid to the extent that the effect of the surface treatment is not impaired. The surface treatment amount in the colloidal metal oxide particle sol solution is preferably 0.05 to 0.50 g / m ^{2 in} terms of the dry weight of the metal oxide particles. If it is less than 0.05 g / m ² , uniform processing is difficult. If it exceeds 0.50 g / m ² , the sensitivity during thermal transfer may decrease.
(Second thermal transfer recording medium)

The second thermal transfer recording medium provided with the metal vapor deposition layer in the present invention has a heat-resistant slipping layer on one surface of the substrate, and at least a release layer, a metal vapor deposition layer, and an adhesive layer on the other surface in this order. It is a recording medium, and a conventionally known thermal transfer recording medium can be used.

As a material for the release layer and the adhesive layer, a conventionally known thermal transfer ink layer made of a heat-meltable or heat-softening vehicle can be used without any particular limitation. As the vehicle, thermoplastic resins and waxes may be used alone or in combination of two or more. As the first-stage thermoplastic resin, the thermoplastic resins listed in the description of the colored layer in the first thermal transfer recording medium may be used alone or in combination of two or more. Moreover, what was hung by the said colored layer description as an additive can be utilized suitably.

The second thermal transfer recording medium has heat resistance between the release layer and the metal vapor deposition layer in order to prevent damage to the base material and the release layer due to heat when the metal vapor deposition layer is deposited. An anchor layer may be provided. Moreover, you may provide the intermediate | middle layer as described in Unexamined-Japanese-Patent No. 2010-5969 between a metal vapor deposition layer and an adhesion layer.

Further, as the anchor layer, an anchor layer conventionally used in a thermal transfer recording medium provided with a metal vapor deposition layer can be used without any particular limitation. Examples of the material constituting the anchor layer include alkyd resins, phenol resins, polyimides, epoxy resins, urethane resins, unsaturated polyester resins, olefinic resins such as polyethylene and polypropylene, polymethyl methacrylate, polyacrylic amide, and the like. Acrylic resins, styrene resins such as polystyrene, vinyl resins such as polyvinyl chloride and polyvinyl acetate, polyether resins such as polyoxymethylene and polyphenylene oxide, polyvinyl butyral resins, nitrocellulose resins, ethylcellulose resins, etc. Resin. These may be used alone or in combination of two or more. From the viewpoint of ensuring heat resistance, it is preferable that the resin is crosslinked and cured with a crosslinking agent such as isocyanate. The thickness of the anchor layer is preferably in the range of 0.2 to 2.0 μm from the viewpoint of fulfilling a function as a base for metal deposition. When the thickness is less than 0.2 μm, the original function is hardly exhibited. If it is thicker than 2.0 μm, the transferability tends to be impaired.

As the metal vapor deposition layer, a metal vapor deposition layer conventionally used in a thermal transfer recording medium provided with a metal vapor deposition layer can be used without any particular limitation.

As the metal of the metal vapor deposition layer, simple substances such as amylnium, zinc, tin, nickel, chromium, titanium, copper, silver, gold, and platinum, a mixture, an alloy, and the like can be used, and aluminum and tin are preferably used. The metal vapor deposition layer can be formed by a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method or a chemical vapor deposition method.

The thickness of the metal vapor deposition layer is preferably 10 to 100 nm, more preferably 15 to 80 nm, from the viewpoint of obtaining a high gloss metal luster. When the thickness is less than 10 nm, visible light is not reflected to the extent that glossiness is obtained. When the thickness exceeds 100 nm, the foil breakage at the time of transfer becomes worse, and the transfer sensitivity is lowered.
(Third thermal transfer recording medium)

The third thermal transfer recording medium provided with the black masking layer in the present invention is a thermal transfer recording medium provided with a heat-resistant slipping layer on one side of the substrate and at least a black masking layer on the other side.

The purpose of image formation with the third thermal transfer recording medium provided with the black concealing layer in the present invention is to provide a transparent image receptor with a heat-resistant slipping layer on one side of the substrate and at least a colored layer on the other side. After forming an image using the first thermal transfer recording medium, a heat-resistant slipping layer is formed on one surface of the substrate, and at least a release layer, a metal vapor deposition layer, and an adhesive layer are formed on the other surface in this order. When the transparent image receiving member is viewed from the surface opposite to the surface on which the transfer is performed in a state where an image is formed by using the second thermal transfer recording medium provided, the light is first and second. This is for the purpose of preventing the image formed on the thermal transfer recording medium 2 from being transmitted and the metallic luster from being weakened, and is unique to this method.

As the black hiding layer, a conventionally known thermal transfer ink layer comprising a heat-meltable or heat-softening vehicle and a colorant can be used without any particular limitation. As the vehicle, for example, the thermoplastic resins and waxes mentioned in the color material-containing adhesive layer of the first thermal transfer recording medium may be used alone, or two or more kinds may be used in combination. . Moreover, you may use an additive suitably for a various objective.

As the colorant for the black masking layer, a black colorant having a low light transmittance is suitably used in order to achieve the object. Examples include black pigments and black dyes such as carbon black, titanium black, and perylene black, and blacks obtained by mixing various organic pigments and dyes. Carbon black is preferable in terms of light transmittance and cost. . The content of the colorant in the colored hiding layer is suitably 20 to 60% by weight.

The thickness of the black masking layer is preferably 0.5 to 2.5 μm. When the thickness is less than 0.5 μm, the original function is hardly exhibited. If it is thicker than 2.5 μm, the transferability tends to be impaired.

In the third thermal transfer recording medium, a release layer may be provided between the base material and the black hiding layer, and an adhesive layer may be provided on the black hiding layer, if necessary. As the release layer and the adhesive layer, a conventionally known heat-sensitive transfer ink layer made of a heat-meltable or heat-softening vehicle can be used without any particular limitation.

The present invention will be described more specifically using the following Examples 1 to 8 and Comparative Examples 1 and 2. In addition, this invention is not restrict | limited by these Examples.

(Preparation of heat-resistant release layer) A composition shown in Table 1 was kneaded to prepare a heat-resistant release layer coating solution, and the thickness after drying on a 4.5 μm PET film used as a substrate was 0.3 μm. It adjusted so that it might become, and it applied and dried on the said base material, and produced the heat resistant peeling layer. In Comparative Example 2, no heat-resistant release layer was provided.

(Heat-resistant release layer surface treatment)
Surface treatment liquids were prepared by mixing materials having the following formulation, and the surface treatment was performed by applying and drying the heat-resistant release layer in the amount of 1.5 g / m ^{2 with} the combinations shown in Table 1.
Colloidal silica sol solution (particle size 10-15 nm, MEK dispersion, solid content 30%)
10 copies
20 parts of solvent (MEK)

(Preparation of colorant-containing adhesive layer) A material having the following formulation is kneaded to prepare a colorant-containing adhesive layer coating solution, adjusted to a thickness of 0.4 μm after drying, and applied onto the heat-resistant release layer. The colorant-containing adhesive layer was laminated on the heat-resistant release layer and then dried.
Polyester resin (softening point 110 ° C.) 42 parts Polymethyl methacrylate resin (Tg 105 ° C., weight average molecular weight Mw 280,000)
42 parts
21 parts of organic pigment
Dispersant 2 parts
225 parts of solvent (MEK)

(Preparation of heat-resistant slipping layer) A material having the following formulation is kneaded to prepare a heat-resistant slipping coating liquid, and the thickness after drying is adjusted to 0.15 μm to adjust the release layer and color of the substrate. The heat-resistant slipping layer was prepared by coating and drying on the surface opposite to the surface on which the material-containing adhesive layer was laminated, and the first thermal transfer recording media of Examples 1-8 and Comparative Examples 1-2 were prepared.
Silicone modified urethane resin 5 parts
Isocyanate (TDI) 3 parts
Solvent (MEK) 140 parts
25 parts of solvent (toluene)

(Preparation of second thermal transfer recording medium)
(Release layer) Prepare a release layer coating solution by kneading the materials of the following formulation, and adjust the thickness after drying to 0.5 μm on the 4.5 μm PET film used as the base material. The release layer was prepared on the substrate by coating and drying.
1 part polyester resin (softening point 110 ° C)
Ketone resin (softening point 80 ° C.) 1 part acrylic resin (Tg 105 ° C., weight average molecular weight Mw 25,000)
73 parts
225 parts of solvent (MEK)

(Anchor layer preparation) An anchor layer coating solution is prepared by kneading the materials of the following formulation, adjusted to a thickness of 0.5 μm after drying, and coated on the release layer and dried to anchor layer Was laminated on a release layer.
21.5 parts of nitrocellulose
Isocyanate (TDI) 16.0 parts acrylic resin (Tg 105 ° C., weight average molecular weight Mw 95,000)
5.5 parts
Solvent (MEK) 57.0 parts

(Metal vapor deposition layer production)
A metal vapor deposition layer was prepared by depositing and stacking tin on the anchor layer so as to have a vapor deposition thickness of 20 nm by vacuum deposition.

(Adhesive layer preparation)
Adhesive layer coating solution is prepared by mixing the materials of the following formulation, adjusted to a thickness of 0.05 μm after drying, and coated on the metal vapor deposition layer and dried to fix the anchor layer on the metal vapor deposition layer. It was produced by laminating.
Polyester resin (softening point 165 ° C) 2.0 parts
Solvent (MEK) 98.0 parts

(Preparation of heat-resistant slip layer)
Adjust the heat-resistant slip coating solution on the surface opposite to the side where the release layer, anchor layer, metal vapor deposition layer, and adhesive layer of the substrate are laminated so that the thickness after drying is 0.15 μm. Then, a heat-resistant slip layer was produced by coating and drying, and a second thermal transfer recording medium was produced.

(Third thermal transfer recording medium production)
(Black masking layer production)
Prepare the adhesive layer coating solution by kneading the materials of the following formulation, and adjust the thickness after drying to 1.5 μm on the 4.5 μm PET film used as the base material. To prepare a black masking layer.
Polyester resin (softening point 110 ° C.) 8 parts Carbon black 10 parts Acrylic resin (Tg 105 ° C., weight average molecular weight Mw 25,000) 8 parts Solvent (MEK) 74 parts

(Preparation of heat-resistant slip layer)
On the surface of the substrate opposite to the black masking layer coated, the heat-resistant slip coating solution is adjusted so that the thickness after drying is 0.15 μm, and is coated and dried. The third heat transfer recording medium was prepared by producing a conductive layer.

The dull evaluation results of each Example and Comparative Example are shown in Table 1, and the dull evaluation method is shown below.

(Dullness evaluation)
An image is formed by a thermal transfer printer on a transparent glass plate having a thickness of 0.5 mm using the first thermal transfer recording media of Examples 1 to 8 and Comparative Examples 1 and 2, and the second thermal transfer recording is formed thereon. The medium is transferred by being superimposed with a thermal transfer printer, and after the third thermal transfer recording medium is transferred with being superimposed on the thermal transfer printer, the glass plate is viewed from the opposite side of the transfer side, The dull state of the colored metallic gloss image was judged visually. Judgment criteria are as follows.
A: The metallic luster is not dull.
○: The metallic luster is slightly dull, but there is no practical problem.
X: The metallic luster is dull and there is a practical problem.
Printer: Canon plate & sheet printer PP500 Plate printing mode (Transfer speed: 30mm / sec)

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密着性付与剤樹脂＊１ ：ポリエステル樹脂 軟化点１１０℃
密着性付与剤樹脂＊２ ：ケトン樹脂 軟化点８０℃
コロイド状シリカゾル液 ：シリカ粒径１０〜１５ｎｍ、固形分３０％ＭＥＫ分散液

Acrylic resin 1: Tg 105 ° C., molecular weight Mw 280,000
Acrylic resin 2: Tg 105 ° C., molecular weight Mw 480,000
Acrylic resin 3: Tg 105 ° C., molecular weight Mw 95,000
Adhesion imparting agent resin * 1: Polyester resin Softening point 110 ° C.
Adhesion imparting agent resin * 2: Ketone resin Softening point 80 ° C
Colloidal silica sol liquid: MEK dispersion with silica particle size of 10-15 nm, solid content 30%

Claims (4)

After forming an image by thermal transfer on a transparent image receptor using a first thermal transfer recording medium provided with a heat-resistant slipping layer on one side of the substrate and at least a colored layer on the other side, An image is formed by thermal transfer using a second thermal transfer recording medium in which a heat-resistant slipping layer is provided on one surface of the substrate and at least a release layer, a metal vapor deposition layer, and an adhesive layer are provided in this order on the other surface. Further, an image is formed by thermal transfer using a third thermal transfer recording medium on which a heat-resistant slipping layer is provided on one side of the substrate and at least a black masking layer is provided on the other side. In the thermal transfer decorating method, the first thermal transfer method is characterized in that a transparent transfer image receiving body is obtained from a surface opposite to the surface on which the transfer has been performed. The recording medium has at least a heat-resistant release layer and a colorant-containing adhesive layer on the other surface. Thermal transfer recording medium comprising a in a thermal transfer recording medium formed by providing. The heat-resistant release layer of the first thermal transfer recording medium is composed of inorganic particles and a binder resin, the content of the inorganic particles is 35% by weight to 80% by weight in the heat-resistant release layer, and the heat-resistant release layer. 2. The thermal transfer recording medium according to claim 1, wherein the total light transmittance of the conductive release layer is 80% or more. The thermal transfer recording medium according to claim 2, wherein the inorganic particles are silica particles. 3. The surface of the heat-resistant release layer of the first thermal transfer recording medium is surface-treated with a colloidal silica sol solution, and the color material-containing adhesive layer is provided thereon. 4. The thermal transfer recording medium according to any one of 3.