JP7183851B2 - Combination of thermal transfer sheet and intermediate transfer medium, and print produced using this - Google Patents

Description

The present invention relates to a combination of a thermal transfer sheet and an intermediate transfer medium, and prints made using the same.

Conventionally, as one embodiment of a method for producing a printed matter, a substrate (hereinafter, the substrate included in the thermal transfer sheet is referred to as the first substrate) and a transfer layer containing a coloring material (hereinafter, the transfer layer included in the thermal transfer sheet) Energy is applied to the thermal transfer sheet using a thermal head or the like to transfer the first transfer layer onto a transfer material such as paper or a resin substrate, thereby forming an image. A thermal fusion transfer method is known in which a printed matter is produced by performing.

Further, as another method for producing a printed matter, a base material (hereinafter, the base material included in the intermediate transfer medium is referred to as the second base material) and a transfer layer including a receiving layer (hereinafter, the transfer layer included in the intermediate transfer medium is referred to as the second base material). After forming an image by transferring a first transfer layer from a thermal transfer sheet onto a receiving layer of an intermediate transfer medium comprising a second transfer layer, the intermediate transfer medium is heated to convert the second transfer layer to a second transfer layer. A method is known in which a transfer layer is transferred onto an object to be transferred.
Prints produced by such methods are generally required to have high scratch resistance. That is, it is required that the adhesion between the first transfer layer and the material to be transferred and the adhesion between the first transfer layer and the receiving layer be high.
In some cases, two or more first transfer layers containing different coloring materials are transferred onto the receiving layer for the purpose of adjusting the hue of the image. It is required that the adhesion between the first transfer layers is high so that there is no such problem.

In addition, from the viewpoint of improving the quality of the image to be produced, it is required that the second transfer layer after image formation can be transferred onto the transfer-receiving material without causing defective transfer portions.

Furthermore, the prints thus produced have high light fastness that does not cause yellowing or the like even when stored for a long period of time under severe conditions such as high temperatures and sunlight irradiation. And it is required to have heat resistance.
For example, Patent Document 1 discloses a thermal transfer sheet provided with a transfer layer containing a vinyl chloride-vinyl acetate copolymer resin having a specific average molecular weight. And there is room for improvement in heat resistance.

Japanese Patent Application Laid-Open No. 2001-219654

The present inventors have found that the above problem can be solved by incorporating a vinyl chloride-vinyl acetate copolymer and a metal soap into the first transfer layer of the thermal transfer sheet and the receiving layer of the intermediate transfer medium. I got some insight.

The present invention has been made based on the above findings, and the problems to be solved are the adhesion between the first transfer layer and the receiving layer, the adhesion between the first transfer layer and the transferred material, Adhesion between the transfer layers (hereinafter collectively referred to as adhesion in some cases) and transferability of the second transfer layer after image formation are high, and a printed matter having high light resistance and heat resistance can be produced. To provide a combination of a thermal transfer sheet and an intermediate transfer medium.
Further, another problem to be solved is to provide a printed material having high scratch resistance, high quality free from transfer defects, etc., and high light resistance and heat resistance.

The combination of the thermal transfer sheet of the present invention and an intermediate transfer medium is
A thermal transfer sheet comprising a first substrate and a first transfer layer,
the first transfer layer contains a coloring material, a vinyl chloride-vinyl acetate copolymer and a metal soap;
an intermediate transfer medium comprising a second substrate and a second transfer layer comprising at least a receiving layer;
The receiving layer is characterized by containing a vinyl chloride-vinyl acetate copolymer and a metallic soap.

In one embodiment, at least one of the first transfer layer and the receiving layer has a metal soap content of 0.1% by mass or more and 10% by mass or less.

In one embodiment, the content of the metallic soap in the first transfer layer is 0.1% by mass or more and 10% by mass or less.

In one embodiment, the content of the metallic soap in the receptive layer is 0.1% by mass or more and 10% by mass or less.

In one embodiment, the metal soap is a metal salt of stearic acid.

In one embodiment, in at least one of the first transfer layer and the receiving layer, the vinyl chloride-vinyl acetate copolymer has a number average molecular weight of 5,000 or more and 50,000 or less.

In one embodiment, the content of the vinyl chloride-vinyl acetate copolymer in the first transfer layer is 30% by mass or more and 70% by mass or less.

In one embodiment, the content of the vinyl chloride-vinyl acetate copolymer in the receiving layer is 50% by mass or more and 99.9% by mass or less.

In one embodiment, the thermal transfer sheet comprises the first transfer layers in a frame-sequential manner.

The printed matter of the present invention is produced by using a combination of the thermal transfer sheet and the intermediate transfer medium,
comprising a material to be transferred, a first transfer layer, and a receiving layer;
The material to be transferred is a resin substrate made of polyvinyl chloride.

According to the present invention, the adhesion between the first transfer layer and the receiving layer, the adhesion between the first transfer layer and the material to be transferred, the adhesion between the first transfer layers, and the adhesion of the second transfer layer after image formation. It is possible to provide a combination of a thermal transfer sheet and an intermediate transfer medium with which a printed matter having high transferability and high lightfastness and heat resistance can be produced.
Further, according to the present invention, it is possible to provide a printed material having high abrasion resistance, high quality free from transfer defects, etc., and high light resistance and heat resistance.

1 is a schematic cross-sectional view showing one embodiment of a thermal transfer sheet constituting the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of a thermal transfer sheet constituting the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of a thermal transfer sheet constituting the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of an intermediate transfer medium constituting the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of an intermediate transfer medium constituting the present invention; FIG. 1 is a schematic cross-sectional view showing one embodiment of an intermediate transfer medium constituting the present invention; FIG. 1 is a schematic cross-sectional view showing an embodiment of a printed matter of the present invention; FIG.

(Thermal transfer sheet)
A thermal transfer sheet 10 constituting the present invention comprises a first substrate 11 and a first transfer layer 12, as shown in FIG.
In one embodiment, the thermal transfer sheet 10 may comprise a plurality of first transfer layers 12A, 12B, 12C, 12D in a frame sequential manner, as shown in FIG.
In one embodiment, as shown in FIG. 3, the thermal transfer sheet 10 may have a back layer 13 on the side of the first substrate 11 opposite to the side on which the first transfer layer 12 is provided.
Each layer included in the thermal transfer sheet will be described below.

(First base material)
The first base material has heat resistance that can withstand thermal energy applied during thermal transfer (for example, heat from a thermal head) and mechanical strength that can support the layer provided on the first base material. Examples of the first substrate include paper substrates such as woodfree paper, art paper, coated paper, resin-coated paper, cast-coated paper, paperboard, synthetic paper and impregnated paper, polyethylene terephthalate (PET), and polybutylene terephthalate (PBT). , polyethylene naphthalate (PEN), 1,4-polycyclohexylene dimethylene terephthalate, polyesters such as terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyamides such as nylon 6 and nylon 6,6, polyethylene (PE) , polyolefins such as polypropylene (PP) and polymethylpentene, vinyl resins such as polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride-vinyl acetate copolymer and polyvinylpyrrolidone (PVP), polyvinyl acetoacetal and Polyvinyl acetal such as polyvinyl butyral, (meth)acrylic resin such as polyacrylate, polymethacrylate and polymethyl methacrylate, imide resin such as polyimide and polyetherimide, cellophane, cellulose acetate, nitrocellulose, cellulose acetate propionate ( CAP) and cellulose acetate butyrate (CAB), styrene resins such as polystyrene (PS), polycarbonates, and resin materials such as ionomer resins (hereinafter simply referred to as "resin films"). Available. The resin film may be a stretched film or an unstretched film, but from the viewpoint of strength, it is preferable to use a stretched film uniaxially or biaxially stretched.
In the present invention, "(meth)acryl" includes both "acryl" and "methacryl".
In the present invention, "(meth)acrylate" includes both "acrylate" and "methacrylate".

Moreover, the above-described laminate consisting of the paper substrate alone, the laminate consisting of the resin film alone, or the laminate of the paper substrate and the resin film can be used as the first substrate.
These laminates can be produced by using a dry lamination method, a wet lamination method, an extrusion method, or the like.

The thickness of the first base material is not particularly limited, and can be, for example, 1 μm or more and 300 μm or less.

(First transfer layer)
The first transfer layer contains a coloring material, a vinyl chloride-vinyl acetate copolymer, and a metal soap, thereby improving the adhesion properties described above, the transfer properties of the second transfer layer after image formation, and the thermal transfer sheet of the present invention. and an intermediate transfer medium can improve the lightfastness and heat resistance of printed matter.

The coloring material is not particularly limited, and can be appropriately selected from carbon black, inorganic pigments, organic pigments and dyes according to the required color tone and the like. Further, the thermal transfer sheet can be provided with a plurality of first transfer layers in a frame-sequential manner, and the plurality of first transfer layers can contain different coloring materials.

The content of the coloring material in the first transfer layer is preferably 30% by mass or more and 70% by mass or less, and more preferably 40% by mass or more and 60% by mass or less. This can improve the image density formed on the receiving layer of the intermediate transfer medium.

In the present invention, vinyl chloride-vinyl acetate copolymer means a copolymer of vinyl chloride and vinyl acetate.
In addition, the vinyl chloride-vinyl acetate copolymer may contain a compound other than vinyl chloride and vinyl acetate as a copolymerization component within a range that does not impair the properties of the present invention. The proportion of structural units derived from other compounds in the vinyl chloride-vinyl acetate copolymer is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. preferable.

The number average molecular weight (Mn) of the vinyl chloride-vinyl acetate copolymer is preferably from 5,000 to 50,000, more preferably from 7,000 to 40,000, and even more preferably from 10,000 to 30,000. As a result, the above-described adhesiveness and the transferability of the second transfer layer after image formation can be further improved.
In the present invention, Mn means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured according to JIS K 7252-1.

The glass transition temperature (Tg) of the vinyl chloride-vinyl acetate copolymer is preferably 50° C. or higher and 90° C. or lower, more preferably 60° C. or higher and 80° C. or lower. As a result, the above-described adhesiveness and the transferability of the second transfer layer after image formation can be further improved.
In the present invention, Tg is a value determined by differential scanning calorimetry (DSC) according to JIS K 7121.

The content of the vinyl chloride-vinyl acetate copolymer in the first transfer layer is preferably 30% by mass or more and 70% by mass or less, more preferably 40% by mass or more and 60% by mass or less. This makes it possible to further improve the above-described adhesiveness and the transferability of the second transfer layer after image formation.

Metallic soaps include, for example, polyvalent metal salts of alkyl phosphates, polyvalent metal salts of fatty acids, and metal salts of alkylcarboxylic acids. Metal salts of acids are preferred. Specific examples of metal soaps include zinc stearate, calcium stearate, barium stearate, magnesium stearate, lead stearate, zinc oleate, zinc laurate, zinc myristate and zinc palmitate.

The content of the metallic soap in the first transfer layer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or more, and 0.5% by mass. More preferably, the content is 3% by mass or less. This makes it possible to further improve the above-described adhesion properties, and the light resistance and heat resistance of printed matter produced by combining the thermal transfer sheet of the present invention with an intermediate transfer medium.

The first transfer layer may contain a resin material other than the vinyl chloride-vinyl acetate copolymer and chimetal soap as long as the characteristics of the present invention are not impaired. Examples include resins, polyurethanes, polyolefins and polyesters.

In addition, the first transfer layer may contain additives such as fillers, plasticizers, antistatic agents, ultraviolet absorbers, inorganic particles, organic particles, release agents, and dispersing agents within the range that does not impair the characteristics of the present invention. can be done.

The thickness of the first transfer layer is preferably 0.3 μm or more and 2 μm or less, more preferably 0.4 μm or more and 1 μm or less. As a result, the adhesion properties, the transfer properties of the second transfer layer after image formation, and the light resistance and heat resistance of printed matter produced by combining the thermal transfer sheet of the present invention with an intermediate transfer medium can be further improved. .

The first transfer layer is formed by dispersing or dissolving the above materials in water or an appropriate solvent to form a coating liquid, which is applied by a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, and a bar coating method. and by a known means such as a rod coating method, to form a coating film on the first base material or the like, and then dry it.

(back layer)
In one embodiment, the thermal transfer sheet comprises a backing layer on the side of the first substrate opposite to the side on which the first transfer layer is provided. Thereby, the blocking resistance of the thermal transfer sheet can be improved.

In one embodiment, the back layer contains one or more resin materials, such as cellulose resin, styrene resin, vinyl resin, polyester, polyurethane, silicone-modified polyurethane, fluorine-modified polyurethane, and (meth)acrylic resin. is mentioned.

In one embodiment, the back layer comprises inorganic or organic particles. This makes it possible to further prevent sticking and wrinkles due to heating during thermal transfer.
Examples of inorganic particles include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, and oxides such as silica. , graphite, saltpeter, and inorganic particles such as boron nitride. The organic particles include organic resin particles made of (meth)acrylic resin, Teflon (registered trademark) resin, silicone resin, lauroyl resin, phenol resin, acetal resin, styrene resin, polyamide, etc., or reacting these with a cross-linking agent. Examples include crosslinked resin particles obtained by

The thickness of the back layer is not particularly limited, and can be, for example, 0.1 μm or more and 2 μm or less.

The back layer is formed by dispersing or dissolving the above material in water or an appropriate solvent, and coating the material by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating and rod coating. , to form a coating film by coating on the first substrate, and then drying the coating film.

(intermediate transfer medium)
An intermediate transfer medium 20 constituting the present invention comprises a second substrate 21 and a second transfer layer 23 comprising at least a receiving layer 22, as shown in FIG.
In one embodiment, the second transfer layer 23 may comprise a release layer 24 below the receptive layer 22, as shown in FIG.
In one embodiment, the second transfer layer 23 included in the intermediate transfer medium 20 may include a protective layer 25 between the receiving layer 22 and the release layer 24, as shown in FIG. Note that the intermediate transfer medium 20 may have a configuration in which the release layer 24 is not provided and the protective layer 25 is provided under the receiving layer 22 .
Each layer included in the intermediate transfer medium 20 will be described below.

(Second base material)
As the base material of the intermediate transfer medium, the same material as the base material of the thermal transfer sheet can be used, and from the viewpoint of strength, it is preferable to use a uniaxially or biaxially stretched film.

The thickness of the second base material is not particularly limited, and can be, for example, 1 μm or more and 300 μm or less.

(Second transfer layer)
The second transfer layer included in the intermediate transfer medium includes at least a receiving layer. Also, in one embodiment, the second transfer layer can comprise a release layer below the receiving layer. Additionally, in one embodiment, the second transfer layer can include a protective layer under the receptive layer or between the release layer and the receptive layer.

(receptive layer)
The receptive layer contains a vinyl chloride-vinyl acetate copolymer and a metal soap, thereby improving the adhesion between the first transfer layer and the receptive layer, the transferability of the second transfer layer after image formation, and the thermal transfer of the present invention. It is possible to improve the light resistance and heat resistance of printed matter produced by combining the sheet and the intermediate transfer medium.

Mn of the vinyl chloride-vinyl acetate copolymer is preferably from 5,000 to 50,000, more preferably from 7,000 to 40,000, and even more preferably from 10,000 to 23,000. Thereby, the adhesion between the first transfer layer and the receptor layer and the transferability of the second transfer layer after image formation can be further improved. Furthermore, it is possible to prevent the occurrence of tailing during the transfer of the second transfer layer (foil tearability). The tailing referred to in the specification of the present application means that when the second transfer layer is transferred onto the transferred object, the boundary between the transfer region and the non-transfer region of the second transfer layer is used as a starting point, and the non-transfer region is drawn from the boundary. It means a phenomenon that the second transfer layer is transferred so as to protrude to the side.

The Tg of the vinyl chloride-vinyl acetate copolymer is preferably 50°C or higher and 90°C or lower, more preferably 60°C or higher and 80°C or lower. Thereby, the adhesion between the first transfer layer and the receptor layer and the transferability of the second transfer layer after image formation can be further improved.

The content of the vinyl chloride-vinyl acetate copolymer in the receptor layer is preferably 50% by mass or more and 99.9% by mass or less, more preferably 70% by mass or more and 99.5% by mass or less, and 90% by mass or more. It is more preferably 99.5% by mass or more, and particularly preferably 96% by mass or more and 99.5% by mass or less. Thereby, the adhesion between the first transfer layer and the receptor layer and the transferability of the second transfer layer after image formation can be further improved.

As the metallic soap in the receiving layer, the same metallic soap as in the first transfer layer can be used. can be improved.

The content of the metallic soap in the receiving layer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.15% by mass or more and 7% by mass or more, and 0.2% by mass or more. % by mass or less is more preferable. As a result, the adhesion between the first transfer layer and the receiving layer, the transferability of the second transfer layer after image formation, and the lightfastness and Heat resistance can be further improved.

The receptor layer may contain resin materials other than vinyl chloride-vinyl acetate copolymers and epoxy resins, such as (meth)acrylic resins, cellulose resins, vinyl resins, polyurethane resins, etc. , polyolefins and polyesters.

In addition, the receiving layer can contain the above-described additives as long as the characteristics of the present invention are not impaired.

The thickness of the receiving layer is preferably 0.5 μm or more and 7 μm or less, more preferably 1 μm or more and 5 μm or less. As a result, the adhesion between the first transfer layer and the receiving layer, the transferability of the second transfer layer after image formation, and the lightfastness and Heat resistance can be further improved.

The receiving layer is prepared by dispersing or dissolving the above materials in water or an appropriate solvent to form a coating liquid, which is applied by roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating and rod coating. It can be formed by coating an intermediate transfer substrate or the like of an intermediate transfer medium by a known means such as a coating method to form a coating film, and drying the film.

(Release layer)
The second transfer layer provided by the intermediate transfer medium can include a release layer below the receiving layer. This can improve the transferability of the second transfer layer after image formation.

In one embodiment, the release layer contains one or more of the resin materials described above.

The content of the resin material in the release layer is preferably 50% by mass or more and 90% by mass or less, and more preferably 70% by mass or more and 85% by mass or less. This can further improve the transferability of the second transfer layer after image formation.

In one embodiment, the release layer includes a resin material such as (meth)acrylic resin, cellulose resin, vinyl resin, polyurethane, silicone resin, and fluororesin.
Also, in one embodiment, the release layer includes natural waxes such as beeswax, spermaceti, Japan wax, rice bran wax, carnauba wax, candelilla wax and montan wax, paraffin waxes, microcrystalline waxes, oxidized waxes, ozokerite, ceresin, esters. Synthetic waxes such as wax and polyethylene wax, higher saturated fatty acids such as margaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, furoic acid and behenic acid, higher saturated monohydric alcohols such as stearyl alcohol and behenyl alcohol, fatty acids of sorbitan Waxes such as higher esters such as esters, higher fatty acid amides such as stearamide and oleic acid amide.
The release layer may contain both the above-described resin material and wax, or may contain two or more of these.

The release layer can contain the above-described additives as long as the properties of the present invention are not impaired.

The thickness of the release layer is preferably 0.5 μm or more and 3 μm or less, more preferably 0.7 μm or more and 2 μm or less. This can further improve the transferability of the second transfer layer after image formation.

The release layer can be formed by dispersing or dissolving the above material in water or an appropriate solvent, followed by known methods such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating and rod coating. It can be formed by applying it on the second base material by means to form a coating film and drying it.

(protective layer)
In one embodiment, the second transfer layer includes a protective layer under the receptive layer or between the receptive layer and the release layer to improve the durability of the prints produced.

The protective layer contains a resin material such as polyester, (meth)acrylic resin, epoxy resin, styrene resin, polyurethane, ionizing radiation curable resin and ultraviolet absorbing resin.

Mn of the resin material contained in the protective layer is preferably 5,000 or more and 30,000 or less, and more preferably 10,000 or more and 25,000 or less. As a result, the durability of the produced print can be further improved.

The Tg of the resin material contained in the protective layer is preferably 40° C. or higher and 90° C. or lower, and more preferably 50° C. or higher and 80° C. or lower. As a result, the durability of the produced print can be further improved.

The content of the resin material in the protective layer is preferably 70% or more and 100% or less, more preferably 75% or more and 99% or less. As a result, the durability of the produced print can be further improved.

The thickness of the protective layer is preferably 0.5 μm or more and 7 μm or less, more preferably 1 μm or more and 5 μm or less. As a result, the durability of the produced print can be further improved.

The protective layer is formed by dispersing or dissolving the above materials in water or an appropriate solvent to form a coating liquid, which is applied by roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating and rod coating. It can be formed by applying it on the second substrate of the intermediate transfer medium to form a coating film by a known means such as a coating method, and drying it.

(printed matter)
A printed matter 30 of the present invention is produced by using a combination of the thermal transfer sheet 10 and the intermediate transfer medium 20. As shown in FIG. , and a receiving layer 22 .
In one embodiment, the print 30 may comprise a release layer 24 or a protective layer 25 and a release layer 24 over the receptive layer 22 .
Hereinafter, a transfer-receiving member included in a print will be described. Since other configurations have been described above, their description is omitted here.

(transferee)
The material to be transferred included in the printed matter of the present invention is not particularly limited, and includes a paper base material similar to the first base material and the second base material, a resin similar to the first base material and the second base material. Materials such as resin substrates, wood, and metal plates can be used as appropriate depending on the application.
Among these, from the viewpoint of transferability of the second transfer layer after image formation, a resin base material composed of polyvinyl chloride is preferable.

The thickness of the material to be transferred is not particularly limited, and is preferably changed as appropriate according to the application. For example, it can be 0.1 mm or more and 2 mm or less.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1
(Production of thermal transfer sheet)
A PET film (Lumirror (registered trademark) manufactured by Toray Industries, Inc.) having a thickness of 4.5 μm was prepared as the first base material. First transfer layer forming coating solutions A, B, C and D having the following compositions were applied in sequence onto one surface of a PET film and dried to form first transfer layers A to D each having a thickness of 0.7 μm. formed.
<Coating Liquid A for Forming First Transfer Layer>
・Phthalocyanine blue 4.9 parts by mass ・Vinyl chloride-vinyl acetate copolymer A (indicated as vinyl chloride acetate in the table) 5 parts by mass (manufactured by Nissin Chemical Industry Co., Ltd., Solbin (registered trademark) CNL, Mn 16000, Tg 76°C)
・Metallic soap A 0.1 part by mass (zinc stearate, manufactured by NI Chemtech Co., Ltd., NS-Z)
・Methyl ethyl ketone (MEK) 90 parts by mass <Coating liquid B for forming the first transfer layer>
・Carmine 6B 4.9 parts by mass ・Vinyl chloride-vinyl acetate copolymer A 5 parts by mass ・Metallic soap A 0.1 parts by mass ・MEK 90 parts by mass <Coating solution C for forming first transfer layer>
・Disazo yellow 4.9 parts by mass ・Vinyl chloride-vinyl acetate copolymer A 5 parts by mass ・Metallic soap A 0.1 parts by mass ・MEK 90 parts by mass <First transfer forming coating liquid D>
・Carbon black 4.9 parts by mass ・Vinyl chloride-vinyl acetate copolymer A 5 parts by mass ・Metal soap A 0.1 parts by mass ・MEK 90 parts by mass

A coating solution for forming a back layer having the following composition was applied to the other surface of the first base material and dried to form a back layer having a thickness of 0.1 μm to obtain a thermal transfer sheet.
<Coating solution for forming back layer>
・Acrylic-modified silicone 10 parts by mass (manufactured by Natoco Co., Ltd., polyalloy NSA-X55)
・ 2 parts by mass of silicone isocyanate (Dialomar (registered trademark) SP901, manufactured by Dainichiseika Kogyo Co., Ltd.)
・MEK 20 parts by mass ・Toluene 20 parts by mass

(Preparation of intermediate transfer medium)
A PET film (Lumirror (registered trademark) manufactured by Toray Industries, Inc.) having a thickness of 12 μm was prepared as the second base material. A release layer-forming coating liquid having the following composition was applied to one surface of a PET film and dried to form a release layer having a thickness of 1 μm.
<Coating solution for forming release layer>
・ (Meth) acrylic resin 9.5 parts by mass (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
・ Polyester 0.5 parts by mass (Toyobo Co., Ltd., Vylon (registered trademark) 200)
・MEK 20 parts by mass ・Toluene 20 parts by mass

A coating solution for forming a protective layer having the following composition was applied onto the release layer and dried to form a protective layer having a thickness of 2 μm.
<Coating solution for forming protective layer>
· Polyester 10 parts by mass (manufactured by Toyobo Co., Ltd., Vylon (registered trademark) 200, Mn 17000, Tg 67 ° C.)
・MEK 20 parts by mass ・Toluene 20 parts by mass

A receiving layer forming coating liquid having the following composition was applied on the protective layer and dried to form a receiving layer having a thickness of 2 μm, thereby obtaining an intermediate transfer medium.
<Coating solution for forming receptor layer>
・Vinyl chloride-vinyl acetate copolymer A 9.9 parts by mass ・Metal soap A 0.1 parts by mass ・MEK 90 parts by mass

Examples 2-10 and Comparative Examples 1-5
A thermal transfer sheet and an intermediate transfer medium were prepared in the same manner as in Example 1, except that at least one of the structure of each first transfer layer provided in the thermal transfer sheet and the structure of each receiving layer provided in the intermediate transfer medium was changed as shown in Table 1. A medium was prepared.
The details of each component in Table 1 are as follows.
・Metallic soap B (calcium stearate, manufactured by NI Chemtech Co., Ltd., NS-A)
・Metallic soap C (barium stearate, manufactured by NI Chemtech Co., Ltd., NS-B)
・Metallic soap D (magnesium stearate, manufactured by NI Chemtech Co., Ltd., NS-M)
・Metallic soap E (lead stearate, manufactured by NI Chemtech Co., Ltd., NSP-R)
- Vinyl chloride-vinyl acetate copolymer B (manufactured by Nissin Chemical Industry Co., Ltd., Solbin (registered trademark) CL, Mn 25000, Tg 70 ° C.)
- Vinyl chloride-vinyl acetate copolymer C (manufactured by Nissin Chemical Industry Co., Ltd., Solbin (registered trademark) CN, Mn 42000, Tg 75 ° C.)
・ (Meth) acrylic resin A (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87)
・ Epoxy resin A (manufactured by Mitsubishi Chemical Corporation, jER1007, epoxy equivalent: 1750 to 2200, Mn2900, softening point 128 ° C.)

<<Transfer test>>
Using a card printer (manufactured by Nippon Data Card Co., Ltd., CR805), the thermal transfer sheet obtained in the above Examples and Comparative Examples was applied onto the receiving layer of the intermediate transfer medium obtained in the above Examples and Comparative Examples. The first transfer layers A to D were transferred in halftone dots to form a half gray solid image of 128/255 gradation. It was observed that there was an overlapping first transfer layer in the half gray solid image.

After image formation, the second transfer layer (receiving layer, protective layer and release layer) of the intermediate transfer medium and the first transfer layer transferred from the thermal transfer sheet are transferred to a polyvinyl chloride card manufactured by Dai Nippon Printing Co., Ltd. (hereinafter referred to as a PVC card) using the above card printer under the conditions of Retransfer Lamination Speed 175 and Retransfer Roller Temp 12 to obtain a print.
A print was also obtained in the same manner under the condition of Retransfer Lamination Speed 165.
The ratio of defective transfer portions in the printed matter was visually determined and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.
In the present invention, the defective transfer portion refers to a portion of the second transfer layer of the intermediate transfer medium to which the image should be originally transferred onto the transfer-receiving material, but is not transferred.
(Evaluation criteria)
A: The percentage of defective transfer portions in the prints produced under the conditions of Retransfer Lamination Speed 165 was 1% or less.
B: The percentage of the defective transfer portion in the printed material prepared under the condition of Retransfer Lamination Speed 165 was more than 1%, but the percentage of the defective transfer portion in the printed material prepared under the condition of Retransfer Lamination Speed 175 was 1% or less. there were.
NG: The percentage of defective transfer portions in the prints produced under the condition of Return Lamination Speed 175 was more than 1%.

<<Adhesion test>>
In the transferability test, the prints made under the conditions of Retransfer Lamination Speed 175 and Retransfer Roller Temp 12 were tested using a Taber tester (abrasion wheel CS-10F) in accordance with ANSI-INCITS322-2002, 5.9 Surface Abrasion. A Taber test method (load of 500 gf, 60 cycles/min., 250 cycles) was performed.
The printed matter after the test was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
In Comparative Example 5, the result of the transferability test was poor, so the adhesion test, light resistance test, heat resistance test and foil cut resistance test were not conducted.
(Evaluation criteria)
A: No abrasion scratches were observed on the printed matter.
B: Slight abrasion scratches were observed on the printed matter, but they were of a degree of practically no problem.
NG: A large number of abrasion scratches were observed on the printed matter, and there was a problem in practical use.

<<Light resistance test>>
In the transferability test, the prints produced under the conditions of Retransfer Lamination Speed 175 and Retransfer Roller Temp 12 were irradiated with light under the following conditions.
(Irradiation conditions)
・ Irradiation tester: Ci4000 manufactured by Atlas
・Light source: xenon lamp ・Inner filter: CIRA
・Outer filter: soda lime ・Black panel temperature: 45℃
・Irradiation intensity measured at a wavelength of 420 nm: 1.2 W / m ²
・Irradiation energy measured at a wavelength of 420 nm: 1000 kJ / m ²

The printed matter after light irradiation was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: No yellowing was observed in the printed matter.
B: Slight yellowing was observed in the printed matter, but it was of a degree of practically no problem.
NG: Much yellowing was observed in the printed matter.

<<Heat resistance test>>
In the transferability test, printed matter prepared under the conditions of Retransfer Lamination Speed 175 and Retransfer Roller Temp 12 was stored in an environment of 60° C. and a relative humidity of 30%.
The printed matter after storage was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: No yellowing was observed in the printed matter.
B: Slight yellowing was observed in the printed matter, but it was of a degree of practically no problem.
NG: Much yellowing was observed in the printed matter.

<<Foil cut resistance test>>
Under the conditions of Retransfer Lamination Speed 175 and Retransfer Roller Temp 12, 10 prints were continuously produced in the same manner as in the transferability test.
The produced prints were visually observed and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: The maximum length of tailing was 0.3 mm or less in 10 prints.
B: In 10 prints, the maximum length of tailing that occurred was more than 0.3 mm and 0.5 mm or less.
C: The maximum length of tailing that occurred was over 0.5 mm in 10 prints.

10: Thermal transfer sheet, 11: First substrate, 12: First transfer layer, 13: Back layer, 20: Intermediate transfer medium, 21: Second substrate, 22: Receiving layer, 23: Second transfer layer, 24 : Release layer 25: Protective layer 30: Printed matter 31 Transferee

Claims (10)

A combination of a thermal transfer sheet and an intermediate transfer medium,
The thermal transfer sheet comprises a first substrate and a first transfer layer,
wherein the first transfer layer contains a coloring material, a vinyl chloride-vinyl acetate copolymer and a metal soap;
said intermediate transfer medium comprising a second substrate and a second transfer layer comprising at least a receiving layer;
A combination thermal transfer sheet and intermediate transfer medium, wherein said receiving layer comprises a vinyl chloride-vinyl acetate copolymer and a metallic soap. 2. The combination of a thermal transfer sheet and an intermediate transfer medium according to claim 1, wherein the content of said metallic soap in at least one of said first transfer layer and said receiving layer is 0.1% by mass or more and 10% by mass or less. . 3. The combination of a thermal transfer sheet and an intermediate transfer medium according to claim 1, wherein the content of said metallic soap in said first transfer layer is 0.1% by mass or more and 10% by mass or less. 4. The combination of a thermal transfer sheet and an intermediate transfer medium according to claim 1, wherein the content of said metal soap in said receiving layer is 0.1% by mass or more and 10% by mass or less. The combination thermal transfer sheet and intermediate transfer medium according to any one of claims 1 to 4, wherein the metallic soap is a metallic salt of stearic acid. The thermal transfer device according to any one of claims 1 to 5, wherein the vinyl chloride-vinyl acetate copolymer in at least one of the first transfer layer and the receiving layer has a number average molecular weight of 5000 or more and 50000 or less. Combination of sheet and intermediate transfer medium. The thermal transfer sheet and the intermediate transfer medium according to any one of claims 1 to 6, wherein the content of the vinyl chloride-vinyl acetate copolymer in the first transfer layer is 30% by mass or more and 70% by mass or less. combination with. The thermal transfer sheet and the intermediate transfer medium according to any one of claims 1 to 7, wherein the content of the vinyl chloride-vinyl acetate copolymer in the receiving layer is 50% by mass or more and 99.9% by mass or less. combination with. The combined thermal transfer sheet and intermediate transfer medium of any one of claims 1 to 8, wherein the thermal transfer sheet comprises the first transfer layers in a frame-sequential manner. A printed matter produced using a combination of the thermal transfer sheet according to any one of claims 1 to 9 and an intermediate transfer medium,
comprising a material to be transferred, the first transfer layer, and the receiving layer;
A printed matter, wherein the material to be transferred is a resin substrate made of polyvinyl chloride.

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