JP2008229955A - Acceptor for thermal transfer recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acceptor for thermal transfer recording, not only in which an image has excellent resistance to organic solvent but also which has a favorable outer appearance making fingerprints unobtrusive. <P>SOLUTION: The acceptor for thermal transfer recording comprises providing an under layer and an accepting layer in the order named on a support made of plastic film with a layer colored in silver, wherein the under layer includes a pigment and a resin and the accepting layer includes a pigment, a resin and a crosslinking agent, the resin included in the under layer is the one obtained by curing an ultraviolet-curing type resin through the irradiation of ultraviolet rays, at least one kind of the resins included in the accepting layer is the metal salt of ethylene-methacrylic acid copolymer, and the 75° glossiness (according to JIS P-8142) of the surface of the accepting layer is 9-25% and its lightness L* (according to JIS Z-8722-1982) is 80-90. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a receptor for thermal transfer recording, and more specifically, a transferred image formed on the receptor is excellent in solvent resistance, and excellent in appearance in which fingerprint marks on the receiving layer are not noticeable even when the receptor is handled with bare hands. The present invention relates to a receptor for thermal transfer recording.

  A method for forming an image by heating a thermal transfer recording medium with a thermal head and transferring ink to a receptor is generally known, and is used for producing labels such as nameplates. When such a label is used in an environment using an organic solvent such as methyl ethyl ketone (MEK), it is required that the image transferred to the label is not erased by such an organic solvent. Further, when used in industrial applications, it is required that the image is not destroyed even when the label surface is rubbed with a strong force.

  As a receptor excellent in ink transfer property and chemical resistance, for example, Patent Documents 1 to 4 show a receptor using an ethylene ionomer resin in a receiving layer. Patent Document 5 discloses a coating layer made of an ethyleneimine adduct of an unsaturated carboxylic acid olefin copolymer and a polyimine polymer. However, it cannot be said that the solvent resistance of the image formed on the receiving layer or coating layer is sufficient.

  Furthermore, in order to obtain the solvent resistance of the transferred image, it has been devised to add the same kind of resin having excellent solvent resistance to the ink and the receiving layer. For example, Patent Document 6 shows that a specific polyolefin is used for the ink resin and the receiving layer. Patent Documents 7 and 8 show that nylon is added to the ink layer and the receiving layer. However, even with these methods, the solvent resistance of an image that can withstand extremely severe use conditions cannot be obtained.

In addition, there is a great need for silver labels that match the color of equipment in the nameplates of transportation equipment and electronic equipment. Of these, matte ones that suppress the gloss of the label surface are often used.
However, the silver matte label has a problem that the appearance is deteriorated because fingerprints are noticeable when handled with bare hands.

  In order to make it difficult to leave a fingerprint mark, Patent Document 9 proposes that the image recording layer be provided with specific irregularities. In addition, for an inkjet receiver, Patent Document 10 proposes that the ink receiving layer contains a specific resin and an inorganic compound. However, none of them achieves both high solvent resistance of the image.

Japanese Patent Laid-Open No. 4-115995 Japanese Patent Laid-Open No. 5-286227 JP-A-8-43994 JP-A-8-58250 JP 2002-113959 A Japanese Patent No. 25333456 JP-A-4-347688 JP 2001-199171 A JP 2006-91808 A Japanese Patent Laid-Open No. 9-169159

  In order to solve the above problems, the present invention has an object to provide a thermal transfer recording receptor having an excellent appearance in which an image has not only excellent resistance to an organic solvent but also traces of fingerprints are not noticeable. And

As a result of intensive studies, the present inventor has found that the above problems can be solved by the following means.
(1) In a thermal transfer recording receiver in which an under layer and a receiving layer are sequentially provided on a support made of a plastic film having a silver-colored layer, the under layer contains a pigment and a resin, A resin containing a pigment, a resin, and a crosslinking agent, and the resin contained in the under layer is a resin obtained by curing an ultraviolet curable resin by ultraviolet irradiation, and at least one of the resins contained in the receiving layer is ethylene-methacrylic acid A metal salt of a copolymer, characterized in that the surface of the receiving layer has a 75 ° gloss (JIS P-8142) of 9-25% and a lightness L * (JIS Z-8722-1982) of 80-90%. A thermal transfer recording receptor.
(2) The receptor for thermal transfer recording as described in (1) above, wherein the receptor layer contains polyethyleneimine.
(3) The thermal transfer recording receiver as described in (1) or (2) above, wherein the pigment of the under layer is an organic pigment.
(4) The receptor for thermal transfer recording according to any one of (1) to (3) above, wherein the smoothness (JIS P-8119) of the surface of the receptor layer is 100 to 2000 seconds.

(5) In a recording method of printing on a thermal transfer recording receptor using a thermal transfer recording medium in which a release layer containing a wax and an ink layer containing a colorant are sequentially laminated on the support,
The ink layer includes a metal salt of an ethylene-methacrylic acid copolymer, and the thermal transfer recording receptor is the silver thermal transfer recording receptor according to any one of (1) to (4) above. Recording method.
(6) A recording material in which an image is formed on a receptor by the recording method of (5) above.

  The thermal transfer recording receptor according to the present invention not only has an excellent resistance to an organic solvent, but also has a good appearance with no noticeable fingerprint marks.

  In a thermal transfer recording receiver in which an under layer and a receiving layer are sequentially provided on a support made of a plastic film having a silver-colored layer, the under layer contains a pigment and a resin, and the receiving layer includes the pigment and the resin. And the crosslinking agent, and the resin contained in the under layer is a resin obtained by curing an ultraviolet curable resin by ultraviolet irradiation, and at least one of the resins contained in the receiving layer is an ethylene-methacrylic acid copolymer Thermal transfer characterized in that the 75 ° gloss (JIS P-8142) of the receiving layer surface is 9-25% and the lightness L * (JIS Z-8722-1982) is 80-90%. A recording receptor is provided.

  The present invention is described in detail below. As described above, the receiver of the present invention is a thermal transfer recording receiver in which an under layer and a receiving layer are sequentially provided on a support made of a plastic film having a silver-colored layer. The receiving layer contains a pigment, a resin and a crosslinking agent, and the resin contained in the under layer is a resin obtained by curing an ultraviolet curable resin by ultraviolet irradiation, and the resin contained in the receiving layer At least one is a metal salt of an ethylene-methacrylic acid copolymer, 75 ° gloss (JIS P-8142) of the receiving layer surface is 9 to 25%, and lightness L * (JIS Z-8722-1982) is 80. It is characterized by -90%. That is, in such a thermal transfer recording receptor, an image transferred onto the thermal transfer recording receptor has excellent resistance to a solvent such as MEK. In addition, by setting the gloss and brightness L * of the receptor surface to a specific range, the receptor can be handled with bare hands, and the fingerprint traces on the receptor layer can be made inconspicuous.

In order to make the glossiness and lightness L * within this range in the present invention, specifically, the gloss of the surface of the layer colored in silver, the particle size of the pigment used in the under layer and the receiving layer, the ratio of resin to pigment The thickness of the under layer and the receiving layer can be adjusted.
In the present invention, the lightness L * can be measured with a specular reflection light removal (SCE) type color difference meter according to JIS Z-8722-1982.

  In the present invention, a plastic film is used as the support for the thermal transfer recording receptor. For example, polyester, polyethylene, polypropylene, polyvinyl chloride, polyethersulfone, polyphenylene sulfide, polyetherimide, polyetheretherketone, polyimide, nylon, vinylon, or other plastic films, or synthetic paper such as polyolefin or polyester are used. It is done. Of these, a polyester film is preferable in terms of strength and price.

In the present invention, a silver colored layer is provided on the support. The layer colored in silver can be prepared, for example, by a method by vapor deposition on a support.
The metal vapor deposition layer is obtained by forming a metal layer on a support by a method such as vacuum vapor deposition, electron beam vapor deposition, sputtering, or the like, such as aluminum, silver, or zinc. Aluminum is preferably used as the metal of the metal vapor deposition layer. Moreover, it is preferable that the thickness of a metal vapor deposition layer shall be 0.01-0.1 micrometer.
In the present invention, it is preferable to use a transparent or translucent plastic film as the support, and to provide a silver-colored layer on the side opposite to the provision of the under layer and the receiving layer. Specifically, the glossiness measured from the surface where the metal vapor deposition layer is not provided is 150 to 750% (JIS Z-8741 (60 ° / 60 °)), and further 550 to 750% (JIS Z-8741). (60 ° / 60 °) is preferably used.

In the present invention, an under layer containing a pigment and a resin is provided between the receiving layer and the support.
Examples of the pigment used in the under layer include inorganic materials such as calcium carbonate, magnesium carbonate, silica, calcium silicate, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, calcined kaolin, and talc. Pigments. Examples thereof include organic pigments such as crosslinked acrylic resin particles such as crosslinked polymethyl methacrylate, benzoguanamine / formaldehyde resin particles, melamine / formaldehyde resin particles, silicone resin particles, and PTFE particles.
Of these, organic pigments are preferably used. The organic pigment is well dispersed in the under layer and a more uniform coating film is obtained, and defects such as omission are less likely to occur in the thermal transfer image. These pigments are used alone or in combination of two or more. The particle size of the pigment preferably used in the under layer is 1.0 to 5.0 μm, and the pigment is contained in the under layer in an amount of 5 to 50% by weight, preferably 10 to 20% by weight.

In the present invention, as the resin used for the under layer, a resin obtained by curing an ultraviolet curable resin by ultraviolet irradiation is used. Of these, urethane acrylate oligomers and / or epoxy acrylate oligomers are preferably used. Moreover, an acrylate monomer can also be added with these oligomers as needed. Further, a sensitizer for increasing the reactivity with ultraviolet rays can be added. As these ultraviolet curable resins, specifically, Unidic manufactured by Dainippon Ink & Chemicals, Inc. can be used.
The under layer resin is preferably contained in the under layer in an amount of 50 to 90% by weight.
In the present invention, the under layer is preferably provided so that the layer thickness is 0.3 to 3.0 μm. If it is less than 0.3 μm, the strength of the under layer is lowered, and if it exceeds 3.0 μm, the solvent resistance of the image is lowered.

The receptor for thermal transfer recording according to the present invention uses an ethylene-methacrylic acid copolymer salt as a binder for the receptor layer. The salt of an ethylene-methacrylic acid copolymer has a structure in which a part of methacrylic acid is crosslinked between molecular chains by cations such as Na, K, Ca, Zn, and NH ₃ . Among these, those containing at least one of Na, K, and Zn are preferable.
In general, an ethylene-methacrylic acid copolymer salt is very difficult to dissolve in a general-purpose solvent. Therefore, in the present invention, it is preferable to use an ethylene-methacrylic acid copolymer salt processed into an aqueous dispersion. Among these, a dispersion in which a salt of an ethylene-methacrylic acid copolymer is self-emulsified without using a dispersant is preferable. In a dispersion emulsified with a dispersant or a water-soluble resin, the dispersant or the water-soluble resin adversely affects the water resistance and solvent resistance of the image.
Examples of such a salt of an ethylene-methacrylic acid copolymer include Chemipearl S-650 and S-659 manufactured by Mitsui Chemicals.
The salt of the ethylene-methacrylic acid copolymer is preferably contained in the receiving layer in an amount of 30 to 90% by weight.

In the present invention, a thermoplastic resin other than the salt of the ethylene-methacrylic acid copolymer can be added to the receptor layer as necessary.
For example, polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, polyvinyl alcohol modified with carboxyl group, carboxylic acid Na group, sulfonic acid Na group, acetoacetyl group, cation group, etc., starch and derivatives thereof , Cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, polyacrylic acid, sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid ternary co Polymer, styrene-maleic anhydride copolymer alkali salt, isobutylene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, ze Water-soluble resin such as latin.
Polyvinyl acetate, polyurethane, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic copolymer, methyl methacrylate-butadiene copolymer, polyacrylate ester, polymethacrylate ester, chloride Vinyl-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, urethane-modified polyethylene, styrene- Examples include acrylic ester copolymers, ethylene-propylene copolymers, ethylene-vinyl chloride copolymers, vinyl acetate-ethylene-vinyl chloride copolymers, emulsions such as polyesters, and water dispersions. These thermoplastic resins are used alone or in combination of two or more.

In order to improve the solvent resistance of the receiving layer, a crosslinking agent is added to the receiving layer.
Examples of the crosslinking agent include carbodiimide, oxazoline, isocyanate, melamine compound, epoxy compound, and polyvalent metal salt. Of these, epoxy compounds are preferred. The crosslinking agent is preferably added in an amount of 3 to 20% by weight based on the resin component.

Pigment is added to the receiving layer. Pigments include calcium carbonate, magnesium carbonate, silica, calcium silicate, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, kaolin, calcined kaolin, talc, etc. Organic pigments such as inorganic pigments, urea-formalin resin, styrene-methacrylic acid ester copolymer resin, polystyrene resin, polyvinylidene chloride resin, polytetrafluoroethylene, and silicone resin can also be added. Of these, calcium carbonate is preferably used. The amount of these pigments added is preferably 30 to 70% by weight in the receiving layer. The pigment preferably has an average particle size of 0.1 to 1.0 μm as observed with an electron microscope.
Furthermore, the receiving layer can contain additives such as lubricants such as higher fatty acid metal salts and paraffin wax, and antifoaming agents, if necessary.

In the present invention, it is preferable to add an ethyleneimine derivative to the receptor layer. By adding an ethyleneimine derivative, it is possible to improve the image resistance particularly to solvents such as MEK, toluene, xylene and the like. Examples of the ethyleneimine derivative include polyethyleneimine, modified polyethyleneimine, and polyethyleneimine-modified acrylic polymer.
The ethyleneimine derivative is preferably added in an amount of 5 to 75% by weight in the receiving layer. If it is less than 5%, the effect of improving the solvent resistance is low, and if it exceeds 75% by weight, the water resistance is lowered. Furthermore, it is particularly preferable to add 20 to 60% by weight in the receiving layer.

  In the present invention, the receiving layer is preferably provided so that the thickness of the receiving layer is 0.3 to 3.0 μm. When the thickness is less than 0.3 μm, the strength of the receiving layer decreases, and when it exceeds 3.0 μm, the solvent resistance of the image decreases. Moreover, it is preferable that the smoothness (JIS P-8119) of the receiving layer surface is 100 to 2000 seconds. If it is less than 100 seconds, the fineness of the image is deteriorated, and if it exceeds 2000 seconds, the solvent resistance of the image is deteriorated. Further, in order to make the trace of the fingerprint inconspicuous, it is preferable to set it for 100 to 400 seconds.

In the present invention, the receptor can be processed into a label that can adhere to the adherend by sequentially laminating an adhesive layer and release paper on the opposite side of the receptor on which the receptor layer is provided. .
In this invention, it is preferable that it is 40-250 micrometers as the whole thickness of a support body, a receiving layer, and the adhesive layer provided as needed. If the thickness is less than 40 μm, the strength of the receptor is lowered and is easily broken, and if it exceeds 250 μm, it is caught when it is attached to an adherend as a label and is easily dropped.

In the recording method for printing an image from a thermal transfer recording medium on the thermal transfer recording receiver of the present invention, a release layer containing a wax, a colorant, and an ink layer containing a salt of an ethylene-methacrylic acid copolymer are formed on a support. When sequentially laminated thermal transfer recording media are used, a transfer image having further excellent solvent resistance can be obtained.
As the salt of the ethylene-methacrylic acid copolymer in the ink layer, the same salt as the salt of the ethylene-methacrylic acid copolymer used for the receiving layer of the thermal transfer recording receptor can be used.

In addition to the metal salt of the ethylene-methacrylic acid copolymer, other resins may be added to the ink layer of the thermal transfer recording medium as necessary.
For example, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, polyvinyl alcohol such as polyvinyl alcohol modified with carboxyl group, sulfonic acid Na group, acetoacetyl group, cationic group, starch and derivatives thereof, methoxycellulose, hydroxy Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, polyacrylic acid, sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid terpolymer, styrene- Water soluble maleic anhydride copolymer alkali salt, isobutylene-maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, etc. Resin.
Polyvinyl acetate, polyurethane, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene-acrylic copolymer, polyacrylic acid, polyacrylic ester, polymethacrylic ester, vinyl chloride-vinyl acetate Polymer, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic acid copolymer, ethylene-vinyl acetate-acrylic acid copolymer, urethane-modified polyethylene, styrene-acrylic acid ester copolymer, ethylene-propylene copolymer , Ethylene-vinyl chloride copolymer, vinyl acetate-ethylene-vinyl chloride copolymer, emulsions such as polyester, water dispersions, and the like.

Various additives may be added to the ink layer as necessary for the purpose of improving thermal transferability and resolution. For example, thermal transferability and resolution can be improved by adding waxy fatty acid amides, various lubricants, synthetic waxes such as paraffin wax, natural waxes such as candelilla wax and carnauba wax. In addition, in this case, resin particles such as silicone resin, tetrafluoroethylene resin, and fluoroalkyl ether resin can be used as the lubricant, in addition to phosphate ester.
As the colorant used in the ink layer, an appropriate one can be selected from carbon black, organic pigments, inorganic pigments or various dyes according to the required color tone.

  A release layer is provided between the support and the ink layer. The release layer preferably contains a resin and a wax as main components. A release layer containing resin and wax as main components facilitates the release of the ink from the support when heat energy is applied from the thermal head, and improves the thermal sensitivity. In the transferred image, the release layer is positioned on the ink layer to protect the ink layer from the solvent.

  As binders to be added to the release layer, ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetal, cellulose derivatives, polyvinyl chloride, polyvinylidene chloride, isoprene rubber, butadiene rubber, ethylene propylene rubber, Butyl rubber, nitrile rubber or the like is used.

  Examples of the wax added to the release layer include beeswax, whale wax, wood wax, rice bran wax, carnauba wax, candelilla wax, montan wax, paraffin wax, polyethylene wax, oxidized polyethylene wax, acid-modified polyethylene wax, and micro wax. Crystalline wax, acid wax, ozokerite, ceresin, ester wax, margaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, furonic acid, behenic acid, stearyl alcohol, behenyl alcohol, sorbitan, stearamide, And oleic acid amide.

  For the support, a known film or paper may be used as it is. For example, a plastic film having relatively high heat resistance such as polyester such as polyethylene terephthalate, polycarbonate, triacetyl cellulose, nylon, polyimide, cellophane, sulfate paper, etc. Preferably used.

  The thermal transfer recording medium may be provided with a protective layer on the back surface of the support, if necessary. The protective layer is a layer to protect the support from high temperature when heat is applied by the thermal head. In addition to high heat resistance thermoplastic resin and thermosetting resin, UV curable resin and electron beam curable resin can also be used. It is. In addition, resin suitable for protective layer formation is a fluororesin, a silicone resin, a polyimide resin, an epoxy resin, a phenol resin, a melamine resin, etc., What is necessary is just to use these resin in a thin film form. Further, since the heat resistance of the support can be remarkably improved by installing the protective layer, a support that has been conventionally unsuitable by installing the layer can also be used.

  The thermal transfer layer described in detail above can be provided by laminating on a support by a hot melt coating method, a coating method using a solvent, or the like. The thermal transfer layer provided by such a coating method may have a total thickness of 0.1 to 10 μm, preferably 0.5 to 6.0 μm. The thickness of each layer is 0.5 to 6.0 μm, preferably 0.8 to 3 μm, and the release layer is 0.2 to 3.0 μm, preferably 1.0 to 2.0 μm. .

  Next, the present invention will be described more specifically with reference to examples. In addition, a part here is a solid content weight reference | standard.

[Example 1]
(1) Preparation of thermal transfer recording medium A polyethylene terephthalate film having a thickness of 4.5 μm is prepared as a support, and silicone rubber (SD7226 manufactured by Toray Dow Corning Silicone Co., Ltd.) is provided on the side opposite to the side on which the thermal transfer recording layer is applied. After drying, the support having a heat resistant slipping layer was prepared by coating and drying so that the coating amount was 0.35 μm.
<Release layer formulation>
Carnauba wax in toluene dispersion (solid content 10%) 90 parts Ethylene-vinyl acetate copolymer resin (vinyl acetate amount 28% by weight)
MFR 15 dg / min) toluene solution (solid content 10%) 10 parts A release layer having the above formulation was applied and dried on the thermal transfer recording layer side of the support so as to have a thickness of 1.0 μm to provide a release layer.
<Ink layer prescription>
Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 62 parts Carbon black aqueous dispersion (solid content 38%) 22 parts Water 16 parts The ink composition having the above composition was applied on the intermediate layer so as to have a thickness of 0.8 μm, and dried. A layer was provided to produce a thermal transfer recording medium.

(2) Preparation of receptor for thermal transfer recording <Under layer prescription>
Urethane acrylate (Dainippon Ink Unidic V-4221) 18 parts 1,2α Hydroxyalkylphenone (radical photopolymerization initiator Ciba Specialty Chemicals) 1 part Silica (Mizusawa Chemical P-527) 6 parts Ethyl acetate 75 parts The underlayer liquid having the above composition was applied and dried on the side of the aluminum vapor-deposited polyester film (Metal Me TS thickness 50 μm) manufactured by Toray Film Co., Ltd. so that the thickness after drying was 1.2 μm. Thereafter, it was cured by treatment with a high-pressure mercury lamp (80 W / cm) for 10 seconds.
<Receptive layer prescription>
Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 18 parts Calcium carbonate (Brilliant-15 average particle size 0.15 μm manufactured by Shiroishi Kogyo) 5 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 0.2 parts Water 76.8 parts The receptor layer solution was dried on the under layer and then coated and dried to a thickness of about 1.0 μm to provide a receptor layer to prepare a thermal transfer recording receptor. The smoothness of the receiving layer surface was 600 seconds.
The surface glossiness was 18% and the lightness L * was 86.
In all the examples and comparative examples, the lightness L * was measured with a spectrophotometric color difference meter SPECTROTOPOMETER CM-3700d (ISO 7724/1 compliant specular light removal (SCE)) manufactured by Minolta.

[Example 2]
A thermal transfer recording receptor was prepared in the same manner as in Example 1 except that the following receptor layer formulation was used in Example 1. The smoothness of the receiving layer surface was 600 seconds. The surface glossiness was 18% and the lightness L * was 86. The same thermal transfer recording medium as in Example 1 was used.
<Receptive layer prescription>
Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 18 parts Calcium carbonate (Brilliant-15 average particle size 0.15 μm made by Shiroishi Kogyo) 5 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 0.2 parts Polyethyleneimine (Epomin made by Nippon Shokubai Co., Ltd.) P-1000 solid content 30%) 3 parts water 73.8 parts

Example 3
A thermal transfer recording medium was prepared in the same manner as in Example 2 except that the following was used as the underlayer formulation in Example 2. The smoothness of the receiving layer surface was 650 seconds. Further, the surface glossiness was 22% and the lightness L * was 84. The same thermal transfer recording medium as in Example 1 was used.
<Under layer prescription>
Urethane Acrylate (Dainippon Ink Unidic V-4221) 18 parts 1,2α-Hydroxyalkylphenone (radical photoinitiator Ciba Specialty Chemicals) 1 part Cross-linked acrylic powder (Soken Chemical MR2HG average particle size 2μm) ) 6 parts ethyl acetate 75 parts

Example 4
A thermal transfer recording medium was prepared in the same manner as in Example 2 except that the following underlayer formulation was used in Example 3 and the thickness after drying was adjusted to 2.5 μm. The smoothness of the receiving layer surface was 350 seconds. The surface glossiness was 9% and the lightness L * was 85. The same thermal transfer recording medium as in Example 1 was used.
<Under layer prescription>
Urethane acrylate (Dainippon Ink Unidic V-4221) 18 parts 1,2α-Hydroxyalkylphenone (radical photopolymerization initiator, Ciba Specialty Chemicals) 1 part Cross-linked acrylic powder (Soken Chemicals MX-500 average particle) Diameter 5μm) 6 parts ethyl acetate 75 parts

[Comparative Example 1]
<Receptive layer prescription>
Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 11 parts Calcium carbonate (Carlite SA average particle size 4.0 μm manufactured by Shiroishi Kogyo) 7 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 0.2 parts Water 80 parts Receiving layer having the above composition The solution was applied and dried to a thickness of 2.5 μm after drying on the side of the aluminum vapor-deposited polyester film (Metal Me TS thickness 50 μm) provided by Toray Film. The smoothness of the receiving layer surface was 750 seconds. The surface glossiness was 6% and the lightness L * was 91. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 2]
<Receptive layer prescription>
Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 13 parts Calcium carbonate slurry (PCX850 manufactured by Shiraishi Kogyo Co., Ltd., average particle size 1.0 μm solid content 27%) 15 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 1 part Polyethyleneimine (manufactured by Nippon Shokubai) Epomin P-1000 (solid content 30%) 7 parts Water 64 parts Receiving layer liquid of the above composition is dried on the side where the aluminum vapor-deposited polyester film (Metal Me TS thickness 50 μm) is provided. The coating was dried to 0.5 μm. The smoothness of the receiving layer surface was 2100 seconds. Further, the surface glossiness was 35%, and the lightness L * was 78. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 3]
<Receptive layer prescription>
Polyester resin water dispersion
(Toyobo's Bironal MD 1335 solid content 30%) 12 parts Calcium carbonate slurry (PCX850, Shiraishi Kogyo average particle size 1.0 μm solid content 27%) 22 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 1 part Water 65 parts The receiving layer solution having the above composition was applied and dried on the side of the aluminum vapor-deposited polyester film (Metal Me TS 50 μm thick) on which the aluminum vapor-deposited layer was provided so that the thickness after drying was 2.5 μm. The smoothness of the receiving layer surface was 1900 seconds. The surface glossiness was 27% and the lightness L * was 83. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 4]
<Under layer prescription>
Salt of ethylene-methacrylic acid copolymer (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 72 parts Epoxy compound (Epoxy equivalent 160 mg / eq Solid content 100%) 1 part Water 27 parts Toray film processed aluminum vapor deposition polyester film (Metal Me TS thickness 50 μm) aluminum vapor deposition The under layer was formed by coating and drying on the side where the layer was not provided so that the thickness after drying was 1.5 μm.
On the under layer, the following receiving layer solution was dried and coated and dried to a thickness of 1.0 μm to form a receiving layer. The smoothness of the receiving layer surface was 2000 seconds. The surface glossiness was 30%, and the lightness L * was 79. The same thermal transfer recording medium as in Example 1 was used.
<Receptive layer prescription>
Calcium carbonate (SL-1000, average particle size 3.0 μm, manufactured by Takehara Chemical) 9 parts Salt of ethylene-methacrylic acid copolymer (Chemical S-650, manufactured by Mitsui Chemicals) 31 parts Epoxy compound (epoxy equivalent 160 mg / eq, solid content 100% ) 1 part Polyethyleneimine (Epomin P-1000 made by Nippon Shokubai 30% solid content) 9 parts Water 50 parts

[Comparative Example 5]
A receptor for thermal transfer recording was prepared in the same manner as in Comparative Example 4 except that the thickness of the receptor layer after drying was 3.0 μm in Comparative Example 4. The smoothness of the receiving layer surface was 950 seconds. The surface glossiness was 27% and the lightness L * was 83. The same thermal transfer recording medium as in Example 1 was used.

[Comparative Example 6]
In Comparative Example 4, a receptor for thermal transfer recording was prepared in the same manner as in Comparative Example 4 except that the following was used as the receiving layer formulation and the thickness after drying was 3.0 μm. The smoothness of the receiving layer surface was 1100 seconds. The surface glossiness was 28% and the lightness L * was 85.
The same thermal transfer recording medium as in Example 1 was used.
<Receptive layer prescription>
Calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., PC average particle size 1.5 μm) 10 parts Ethylene-methacrylic acid copolymer salt (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 36 parts Epoxy compound (epoxy equivalent 160 mg / eq solid content 100%) 1 part Polyethyleneimine (Nippon Shokubai Epomin P-1000 solid content 30%) 9 parts Water 44 parts

[Comparative Example 7]
<Under layer prescription>
Urethane acrylate (Dainippon Ink Unidic V-4221) 16 parts 1,2α hydroxyalkylphenone (radical photopolymerization initiator Ciba Specialty Chemicals) 1 part Silica (Mizusawa Chemical P-603) 4 parts MEK 79 Part The underlayer liquid having the above composition was applied and dried on the side of the aluminum vapor-deposited polyester film (Metal Me TS 50 μm thick) on which the aluminum vapor-deposited layer was not provided, so that the thickness after drying was 1.5 μm. Thereafter, it was cured by treatment with a high-pressure mercury lamp (80 W / cm) for 10 seconds.
On this under layer, the following receiving layer formulation was applied and dried to a thickness of 2.5 μm after drying to prepare a thermal transfer recording receptor. The smoothness of the receiving layer surface was 650 seconds. The surface glossiness was 16% and the lightness L * was 91.
The same thermal transfer recording medium as in Example 1 was used.
<Receptive layer prescription>
Calcium carbonate (SS # 80, average particle size 2.6 μm, manufactured by Nitto Flour Industries) 4 parts Salt of ethylene-methacrylic acid copolymer (Chemical S-650, Mitsui Chemicals)
(Solid content 27%) 15 parts Epoxy compound (Epoxy equivalent 160 mg / eq Solid content 100%) 1 part Polyethyleneimine (Epomin P-1000 made by Nippon Shokubai) (Solid content 30%) 3 parts Water 77 parts

Using the thermal transfer recording medium and the thermal transfer recording receptor obtained as described above, an evaluation test was performed by the following method. Printing was evaluated under the following conditions.
(Printing conditions)
Printer: 96XiIII manufactured by Zebra
Printing speed: 2 inches / second Printing energy: Tone 26

The various characteristics evaluated are as follows.
(1) Solvent resistance After applying 0.5 cc of a solvent to a cotton swab and applying it to a transfer image, the sample was rubbed 30 times with a load of 100 g / cm ² , and the image was observed and evaluated according to the following criteria. Xylene was used as the solvent.
6 As a result of the love test, there is no change from before the test.
5 As a result of the love test, the image can be read, but it can be slightly scratched.
4 As a result of the love test, the image can be read but slightly damaged.
3 As a result of the love test, the image can be read but can be damaged.
2 As a result of the love test, the image remains but cannot be read.
1 As a result of the love test, the image is completely erased.
(2) Traces of fingerprints Fingerprints were placed on the surface of the receptor layer of the receptor with thumbs, and it was visually determined whether the traces were noticeable.

  The above evaluation results are shown in Table 1.

  It can be seen from Table 1 that the thermal transfer recording receivers of the examples have not only excellent resistance to xylene, but also a good appearance with no noticeable fingerprint marks.

Claims (6)

  In a thermal transfer recording receiver in which an under layer and a receiving layer are sequentially provided on a support made of a plastic film having a silver-colored layer, the under layer contains a pigment and a resin, and the receiving layer includes the pigment and the resin. And the crosslinking agent, and the resin contained in the under layer is a resin obtained by curing an ultraviolet curable resin by ultraviolet irradiation, and at least one of the resins contained in the receiving layer is an ethylene-methacrylic acid copolymer Thermal transfer characterized in that the surface of the receiving layer has a 75 ° gloss (JIS P-8142) of 9-25% and a lightness L * (JIS Z-8722-1982) of 80-90%. Receptor for recording.   2. The thermal transfer recording receptor according to claim 1, wherein the receiving layer contains polyethyleneimine.   3. The thermal transfer recording receiver according to claim 1, wherein the pigment of the under layer is an organic pigment.   The receptor for thermal transfer recording according to any one of claims 1 to 3, wherein the smoothness (JIS P-8119) of the surface of the receiving layer is 100 to 2000 seconds. In a recording method of printing on a thermal transfer recording receptor using a thermal transfer recording medium in which a release layer containing wax and an ink layer containing a colorant are sequentially laminated on the support,
The recording method, wherein the ink layer contains a metal salt of an ethylene-methacrylic acid copolymer, and the thermal transfer recording receptor is the silver thermal transfer recording receptor according to any one of claims 1 to 4. .   6. A recording material wherein an image is formed on a receptor by the recording method of claim 5.