JP2015196275A - Set of thermal transfer ink sheet and thermal transfer image receiving sheet and image formation method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a set of a thermal transfer ink sheet and a thermal transfer image receiving sheet, capable of obtaining sufficient print density and improving light fastness of a printed material while suppressing catalytic fading, and to provide an image formation method using the same.SOLUTION: A set includes: a thermal transfer ink sheet having a yellow coloring material layer, a magenta coloring material layer and a cyan coloring material layer including a kind of dye on a substrate sheet; and a thermal transfer image receiving sheet 10 having a particle inclusion layer 12 containing a hollow particle and/or microballoon, and a reception layer 13 on a substrate 11.

Description

  The present invention relates to a set of a thermal transfer ink sheet and a thermal transfer image receiving sheet and an image forming method using the same, and more specifically, a thermal transfer ink sheet comprising a thermal transferable color material layer containing a specific dye, and a specific layer The present invention relates to a method for forming an image using a thermal transfer image receiving sheet having a configuration.

  Conventionally, various printing methods are known. Among them, the thermal diffusion type transfer method (sublimation type thermal transfer method) uses a sublimation dye as a color material, so that density gradation can be freely adjusted, and intermediate colors and gradations can be adjusted. It has excellent tone reproducibility and can form high-quality images comparable to silver halide photographs.

  This thermal diffusion transfer system is a method in which a thermal transfer ink sheet containing a dye (sublimation dye) and a thermal transfer image receiving sheet are superposed, and then the ink sheet is heated by a thermal head whose heat generation is controlled by an electrical signal. The dye in the ink sheet is transferred to the image receiving sheet to record image information. As such thermal diffusion transfer systems become widespread, the printing speed has been increased. Even if conventional thermal energy is printed using a conventional thermal transfer ink sheet and thermal transfer image receiving sheet, a sufficient print density can be obtained. There are problems such as inability to obtain.

  Conventionally, new dyes have been developed in order to improve image storability, but those that sufficiently satisfy both the storability and print density of printed matter have not been developed. Furthermore, when an image is formed using a single dye, there is a problem that the light resistance is poor when combined with other dyes in the image layer (catalytic fading) even if the light resistance is sufficient. It has become. In order to solve such a problem, a thermal transfer sheet in which a specific yellow dye layer and a specific magenta dye layer are formed has been proposed (see, for example, Patent Document 1).

JP 2007-290343 A

  The present invention has been made in view of the background art described above, and an object of the present invention is to obtain a sufficient printing density and to improve the light resistance of the printed matter by suppressing catalytic fading. Another object is to provide a set of a thermal transfer ink sheet and a thermal transfer image receiving sheet. It is another object of the present invention to provide an image forming method capable of obtaining a sufficient printing density and improving the light resistance of a printed matter by suppressing catalytic fading.

  As a result of intensive studies to solve the above problems, the present inventors have used a thermal transfer ink sheet comprising a thermal transferable color material layer containing a specific dye, and a thermal transfer image receiving sheet having a specific layer configuration. The present inventors have found that the above problems can be solved by forming an image on the thermal transfer image receiving sheet. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A set of a thermal transfer ink sheet comprising a yellow color material layer, a magenta color material layer, and a cyan color material layer on a substrate sheet, and a thermal transfer image receiving sheet comprising a particle-containing layer and a receiving layer on the substrate. There,
The yellow color material layer comprises a dye represented by the general formula (I), and the cyan color material layer comprises a dye represented by the general formula (VI);
There is provided a set of a thermal transfer ink sheet and a thermal transfer image receiving sheet, wherein the particle-containing layer comprises hollow particles and / or microballoons.

In an embodiment of the present invention, ring A in the general formula (I) is a methyl group-substituted or unsubstituted aryl group, and R ¹ and R ² each independently have 1 to 5 carbon atoms. The following linear or branched alkyl groups which may be substituted, R ³ is an amino group substituted with a methoxy group, an ethoxy group, or a methyl group or an ethyl group, and R ⁴ is An aryl group which may be substituted;
Ring A in the general formula (VI) is an aryl group substituted with a methyl group, and R27 and R28 each independently have a linear or branched substituent having 1 to 8 carbon atoms. It is preferably an alkyl group that may be used.

  In the embodiment of the present invention, it is preferable that the magenta color material layer contains at least one dye selected from the group consisting of dyes represented by the general formula (IV) and the general formula (X).

  In the aspect of the present invention, it is preferable that the magenta color material layer further includes at least one dye selected from the group consisting of dyes represented by the general formula (VII) and the general formula (VIII). .

  In the aspect of the present invention, it is preferable that the cyan color material layer further includes at least one dye selected from the group consisting of dyes represented by the general formula (IX) and the general formula (XI). .

  In the aspect of the present invention, it is preferable that the thermal transfer ink sheet further includes a color material primer layer between the base material layer and the color material layer of each color.

According to another aspect of the invention,
Preparing a thermal transfer ink sheet comprising a yellow color material layer, a magenta color material layer, and a cyan color material layer on a base material sheet;
Preparing a thermal transfer image-receiving sheet comprising a particle-containing layer and a receiving layer in order on a substrate;
Superposing the color material layer surface of the thermal transfer ink sheet and the receiving layer surface of the thermal transfer image receiving sheet, thermally transferring the color material layer onto the receiving layer, and forming an image on the thermal transfer image receiving sheet;
Comprising
The yellow color material layer comprises a dye represented by the general formula (I), and the cyan color material layer comprises a dye represented by the general formula (VI);
There is provided an image forming method in which the particle-containing layer comprises hollow particles and / or microballoons.

  According to the set of the thermal transfer ink sheet and the thermal transfer image receiving sheet of the present invention, a sufficient print density can be obtained, and the light fastness of the printed matter can be improved by suppressing the catalytic fading. Further, according to the image forming method of the present invention, a sufficient print density can be obtained, and the light fastness of the printed matter can be improved by suppressing the catalytic fading.

1 is a schematic cross-sectional view showing an embodiment of a thermal transfer image receiving sheet used in the present invention. It is the schematic cross section which showed one Embodiment of the thermal transfer ink sheet used by this invention.

Thermal transfer image-receiving sheet The thermal transfer image-receiving sheet of the present invention is obtained by laminating a base material, a particle-containing layer, and a receiving layer on the base material in this order. In a preferred embodiment, the thermal transfer image-receiving sheet may further have a primer layer between the particle-containing layer and the receiving layer, and may further have a back layer on the surface opposite to the receiving layer.

  A schematic cross-sectional view of one embodiment of a thermal transfer image receiving sheet according to the present invention is shown in FIG. A thermal transfer image receiving sheet 10 shown in FIG. 1 is formed by laminating a base material 11, a particle-containing layer 12, and a receiving layer 13 on the base material 11 in this order. Hereinafter, each layer constituting the thermal transfer image receiving sheet according to the present invention will be described.

Substrate In the present invention, the substrate has a role of holding the particle-containing layer and the receiving layer, and heat is applied at the time of thermal transfer, so that it has a mechanical strength that does not hinder handling even in a heated state. It is preferable that it is the material which has.

  Examples of the base material include condenser paper, glassine paper, sulfuric acid paper, high-size paper, synthetic paper (polyolefin-based, polystyrene-based), high-quality paper, art paper, coated paper, and resin-coated paper. , Cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, or polyester, polyacrylate, polycarbonate, polyurethane, polyimide, polyether Imide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone Examples include polyether sulfone, tetrafluoroethylene, perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene, polychlorotrifluoroethylene, and polyvinylidene fluoride. A white opaque film formed by adding a white pigment or a filler to these synthetic resins can also be used, and is not particularly limited. Moreover, the laminated body by the arbitrary combinations of the said base material can also be used. Examples of typical laminates include cellulose fiber paper and synthetic paper, or synthetic paper of cellulose synthetic paper and a plastic film. In this invention, a commercially available base material can also be used, for example, RC paper (Mitsubishi Paper Co., Ltd. make, brand name) etc. are preferable. The base material thickness can be appropriately changed according to the strength and heat resistance required for the thermal transfer image-receiving sheet and the material of the material employed as the base material. Specifically, the base material thickness is 50 μm. It is preferably in the range of 1000 μm or less and more preferably in the range of 100 μm or more and 300 μm or less.

Receiving layer The receiving layer in the present invention receives the sublimation dye transferred from the thermal transfer ink sheet during image formation by thermal transfer, and holds the received sublimation dye in the receiving layer, whereby an image is formed on the surface of the receiving layer. Can be formed and maintained. The receiving layer preferably contains a binder resin and a release agent, and may further contain a wax additive or a urethane-associative thickener.

  Binder resins contained in the receiving layer include acrylic resins, vinyl chloride resins, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers (vinyl acetate resin), poly Halogenated polymers such as vinylidene chloride, vinyl polymers such as polyvinyl acetate and polyacrylates, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, olefins such as ethylene and propylene, and other Examples thereof include copolymer resins with vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, and polycarbonates. In particular, it is preferable to use at least one selected from the group consisting of a vinyl chloride resin, a polyester resin, and an acrylic resin.

  Examples of the release agent contained in the receiving layer include silicone dispersions (including reactive curable silicones), phosphate ester plasticizers, and fluorine compounds, and silicone dispersions are particularly preferable. Various modified silicones such as dimethyl silicone can be used as the silicone dispersion. Specifically, amino-modified silicone, epoxy-modified silicone, alcohol-modified silicone, vinyl-modified silicone, urethane-modified silicone, polyester-modified silicone, polyether-modified silicone, polyester-modified silicone dispersion, acrylic-modified silicone, amide-modified silicone, etc. are used. These can also be mixed or polymerized using various reactions. Two or more release agents may be mixed and used. By using such a release agent, problems such as fusion between the thermal transfer ink sheet and the receiving layer of the thermal transfer image receiving sheet and a decrease in printing sensitivity during printing can be improved. In the present invention, it is particularly preferable to use a polyether-modified silicone type release agent. Two or more polyether-modified silicone mold release agents may be used, or other mold release agents may be used in combination. In the present invention, a commercially available release agent can also be used. X-22-163, X-22-163A, X-22-173DX, X-22-343, X22-3000T, KF-101, KF- 102, KF-106 and KF410 (above, manufactured by Shin-Etsu Chemical Co., Ltd.). Use of such silicone is preferable from the viewpoint of combination with the binder resin.

  Examples of the wax additive contained in the receiving layer include carnauba wax and paraffin wax, and these may be used alone or in combination. In the present invention, the carnauba wax includes natural carnauba wax and purified products and derivatives thereof, including those modified with additives and the like. According to a preferred embodiment, the melting point of carnauba wax is 80 ° C. or more and 90 ° C. or less, the acid value is 10 mg · KOH / g or less, and the saponification value is 78 mg · KOH / g or more and 88 mg · KOH / g or less. The paraffin wax includes natural paraffin wax and purified products and derivatives thereof, and those modified with additives and the like. The melting point of the paraffin wax is preferably 40 ° C. or higher and 105 ° C. or lower, more preferably 40 ° C. or higher and 90 ° C. or lower, and further preferably 40 ° C. or higher and 75 ° C. or lower.

The urethane associative thickener contained in the receiving layer has a viscosity when measured at a liquid temperature of 25 ° C. according to JIS Z8803 using a B-type viscometer when the solid concentration is 30%. Preferably, it is 1000 mPa · s or more and 100,000 mPa · s or less, and more preferably 2000 mPa · s or more and 60000 mPa · s or less. Furthermore, the viscosity ratio is the following formula (1):
Viscosity ratio = V _30,6 / V _30,60 (1)
_{(Wherein, V 30,6} by using a B-type viscometer, in conformity with JIS Z8803, a viscosity (mPa.s) when the rotational speed 6rpm at a liquid temperature 25 ° _{C., V 30, 60} is B Using a viscometer, the viscosity (mPa.s) at a liquid temperature of 25 ° C. and a rotational speed of 60 rpm is shown in accordance with JIS Z8803)
It is preferably 2.0 or more and 5.0 or less, more preferably 2.0 or more and 4.5 or less. This viscosity ratio is generally called a thixotropy index (TI) and is an index that correlates with sagging difficulty. By using a urethane associative thickener with a viscosity and a viscosity ratio in the above range, it gives leveling viscosity to the coating solution for the receiving layer, improves surface quality, and exists in the form of particles. Binders are bound together to form a film, and heat fusion during image printing can be suppressed.

  The content of the urethane associative thickener is preferably 5% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 15% by mass or less, based on the solid content mass of the binder resin of the receiving layer. When the content of the urethane associative thickener is within the above range, the receptor layer can be sufficiently formed, and heat fusion during image printing can be suppressed. In the present invention, a commercially available urethane associative thickener can also be used. For example, UH-450, UH-526, UH-530, UH-540, UH-550 (above, manufactured by ADEKA Corporation), SN thickener A812 (manufactured by San Nopco) is preferable.

Particle-containing layer The particle-containing layer in the present invention has a heat insulating property capable of preventing heat applied during image formation by thermal transfer from being lost due to heat transfer to a substrate or the like. The particle-containing layer contains hollow particles and / or microballoons, and may further contain a hydrophilic binder and other additives. According to a preferred embodiment, the particle-containing layer may be composed of two or more layers. By including hollow particles and / or microballoons in the particle-containing layer, since the solid matter is contained in the resin, the dye can easily penetrate deeply. That is, the relative distance between the first color material transferred to the thermal transfer image receiving sheet and the third color material is increased. As a result, catalytic fading can be further prevented. Furthermore, the effect of preventing catalytic fading can be promoted by using a color material primer that increases sensitivity.

In addition, the particle-containing layer includes cushioning properties by including hollow particles and / or microballoons. Here, the degree of cushioning property of the particle-containing layer can be appropriately adjusted according to the application of the thermal transfer image-receiving sheet. The degree of cushioning of the particle-containing layer can also be adjusted to an arbitrary range by changing the thickness of the particle-containing layer, for example. The thickness of the particle-containing layer is not particularly limited as long as the heat insulating property, cushioning property and the like can be adjusted to a desired level, but preferably in the range of 10 μm to 100 μm, preferably 10 μm to 50 μm. More preferably within the following range. The density of the particle-containing layer is, for example, in the range of 0.1 g / cm ³ or more and 0.8 g / cm ³ or less, and in particular, in the range of 0.2 g / cm ³ or more and 0.7 g / cm ³ or less. Is preferred.

  The average particle diameter of the hollow particles used in the present invention is preferably 0.1 μm or more and 10 μm or less, more preferably 0.3 μm or more and 5 μm or less. If the average particle diameter of the hollow particles is in the above range, heat insulating properties and cushioning properties can be imparted to the particle-containing layer. In the present invention, the volume average particle diameter of the hollow particles can be measured by a conventionally known method such as the Coulter method (Sysmex FPIA-3000 by Malvern). Further, the average hollowness of the hollow particles is preferably 20% or more, more preferably 30% or more and 80% or less. When the average hollowness of the hollow particles is in the above range, heat insulating properties and cushioning properties can be imparted to the particle-containing layer. Furthermore, the organic hollow particle comprised from resin etc. may be sufficient, and the inorganic hollow particle comprised from glass etc. may be sufficient. The hollow particles may be cross-linked hollow particles. In the present invention, commercially available hollow particles can be used. For example, Ropeke HP-1055, Ropeke HP-91, Ropeke OP-84J, Ropeke Ultra, Ropeke SE, and Ropeke ST (Rohm and Haas Co., Ltd.) ), Nipol MH-5055 (Nippon Zeon Corporation), SX8782 and SX866 (JSR Corporation) are preferred. By using such hollow particles, not only the effect of preventing catalytic fading but also the effect of increasing the print density can be promoted.

  In the present invention, commercially available microballoons can also be used, and examples thereof include trade names: FN-80GS, F-30, F-48, F-50, FN-100SS, manufactured by Matsumoto Yushi Co., Ltd. .

Other Layers The thermal transfer image receiving sheet of the present invention may further have other layers other than the above layers. In a preferred embodiment, the thermal transfer image-receiving sheet can further have other layers such as a primer layer, an intermediate layer, and a release layer on the receiving layer side. Moreover, it can have a back surface layer on the opposite side to a receiving layer.

Primer layer The primer layer in the present invention has a role of satisfactorily adhering the particle-containing layer and the receiving layer, and prevents the dye from moving to the particle-containing layer side in a high-temperature and high-humidity environment, thereby improving image storage stability. It has a function to improve. In a preferred embodiment, the primer layer contains hollow particles, a resin, and a hydrophilic binder, and the resin preferably contains an acrylic resin. Although it does not specifically limit as thickness of a primer layer, For example, it is preferable that they are 1 micrometer or more and 40 micrometers or less, 1 micrometer or more and 20 micrometers or less are more preferable, and 1 micrometer or more and 10 micrometers or less are more preferable.

  In the present invention, the acrylic resin refers to a polymer of acrylic acid or methacrylic acid monomer or derivative thereof, a polymer of acrylic acid ester or methacrylic acid ester monomer or derivative thereof, acrylic acid or methacrylic acid monomer and other derivatives. It includes a copolymer with a monomer or a derivative thereof, and a copolymer of a monomer of an acrylate ester or a methacrylate ester with another monomer or a derivative thereof.

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

  According to a preferred embodiment of the present invention, the hydrophilic binder contained in the particle-containing layer or the primer layer includes gelatin and its derivatives, polyvinyl alcohol, polyethylene oxyside, polyvinyl pyrrolidone, pullulan, carboxymethyl cellulose, hydroxyethyl cellulose. Dextran, dextrin, polyacrylic acid and salts thereof, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan, casein, xanthene gum, locust bean gum, alginic acid, and gum arabic, with gelatin being particularly preferred. . By using such a hydrophilic binder, interlayer adhesion of each layer can be improved. In particular, when each layer is formed by an aqueous coating method and a simultaneous multilayer coating method, by using gelatin, the viscosity of each coating solution can be adjusted to a desired range, and a desired film thickness can be obtained. In the present invention, commercially available gelatin can also be used. For example, RR, R, CLV, and N1236 (manufactured by Nitta Gelatin Co., Ltd.) are preferable.

Intermediate Layer In the present invention, at least one intermediate layer may be provided between the particle-containing layer and the primer layer or between the primer layer and the receiving layer. The intermediate layer can be formed using a resin similar to the resin forming the primer layer. By providing an intermediate layer, functions such as solvent resistance, dye diffusion barrier during image storage under high temperature / high humidity, interlayer adhesion, white color imparting, glare / unevenness of the substrate, and antistatic functions are added. Can do. As a method for forming the intermediate layer, known means can be used. For example, an optical brightener, inorganic fine particles, hollow fine particles, and an organic conductive material such as a conductive filler or polyaniline sulfonic acid are added to the intermediate layer. The method of doing is mentioned.

Release layer In the present invention, the release agent may not be added to the receiving layer, but may be provided as a separate release layer on the receiving layer.

Back layer The back layer in the present invention has the fixability of ink used in an ink jet method, a dot impact method, a writing instrument, and the like, and enables a back print excellent in quick-drying with less bleeding of the recording portion ( To improve the backprint suitability). Furthermore, it also has the basic characteristics as the image receiving paper back side described below.
1. When superposed on the receiving layer surface, no sticking (blocking) occurs even if it is stored under a temperature or load.
2. Even when the paper is mistakenly mounted on the printer with the front and back sides reversed, and the thermal transfer sheet is superposed on the thermal transfer sheet, it will stick to the thermal transfer sheet and will not clog in the printer, and the printed matter will be discharged. (Has back surface releasability).
The back layer preferably contains a binder resin and inorganic fine particles, and other additives such as an antifoaming agent and an antistatic agent can be appropriately added to the back layer. In recent years, a water-based coating method is preferred from the viewpoint of environmental considerations, but the back layer of the present invention can be particularly suitably used as the back surface of an image receiving paper on which a receiving layer is formed by a water-based coating method.

  The binder resin contained in the back layer is at least one selected from the group consisting of styrene / acrylic resins, polyester resins, polyurethane resins, and acrylic resins. By using such a binder resin, it is possible to have good adhesion to the base material and good backprint suitability. In the present invention, a commercially available binder resin can also be used, such as Bironal MD 1500 (manufactured by Toyobo Co., Ltd.), Plus Coat Z690 (manufactured by Kyoyo Chemical Co., Ltd.), Superflex 130 (Daiichi Kogyo Seiyaku ( Etc.) are preferable.

  The inorganic fine particles contained in the back layer are at least one selected from the group consisting of colloidal alumina, colloidal silica, and silica particles. By using such inorganic fine particles, it is possible to improve the backprint suitability and prevent blocking.

In the present invention, the coating amount of the back layer is not particularly limited, but the coating amount is preferably within a range of 0.1 g / m ² or more and 3.0 g / m ² or less after drying, and 0.3 g More preferably, it is in the range of not less than / m ^{2 and not} more than 1.5 g / m ² . If the coating amount is in the above range, sufficient back print suitability can be obtained.

Manufacturing Method of Thermal Transfer Image Receiving Sheet A known manufacturing method can be used for manufacturing the thermal transfer image receiving sheet of the present invention. For applying each layer of the thermal transfer image-receiving sheet, known methods such as roll coating, bar coating, gravure coating, gravure reverse coating, die coating, slide coating, and curtain coating can be used. In the present invention, it is preferable to form all the layers constituting the receiving layer from the heat insulating layer on the side having the receiving layer by aqueous coating. Furthermore, it is more preferable to form by all layer aqueous | water-based application | coating which comprises the surface side which has a receiving layer.

Thermal transfer ink sheet The thermal transfer ink sheet (also referred to as ink ribbon) used with the thermal transfer image receiving sheet of the present invention is provided with a three-color heat transferable color material layer on one surface of the base sheet, and the other of the base sheet. What has the layer structure by which the heat-resistant slipping layer is provided in the surface is good. Furthermore, a color material primer layer may be further provided between the base material sheet and the color material layer of each color. According to a preferred embodiment, as shown in FIG. 2, a color material primer layer 22 is formed on one surface of the base material sheet 21, and a yellow color material layer 24, a magenta color material layer 25, and There is provided a thermal transfer ink sheet having a heat transferable color material layer 23 composed of a cyan color material layer 26 and having a heat resistant slipping layer 27 on the other surface. Hereinafter, each layer constituting the thermal transfer ink sheet will be described.

As the material of the base sheet constituting the thermal transfer ink sheet used in the present invention, a conventionally known material can be used, and even if it is other than that, it has a certain degree of heat resistance and strength. Can be used. For example, polyethylene terephthalate, polyester, polypropylene, polycarbonate, polyethylene, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyimide, nylon, cellulose acetate, ionomer and other resin films, condenser paper, paraffin paper, and other non-woven fabrics Etc. These may be used alone, or a laminate in which these are arbitrarily combined may be used. Among these, polyethylene terephthalate which is a versatile plastic that can be thinned and is inexpensive is preferable.

  The thickness of the base sheet can be appropriately selected according to the material so that the strength, heat resistance and the like are appropriate, but usually it is preferably about 0.5 μm to 50 μm, more preferably 1 μm to 20 μm. More preferably, it is 1 μm or more and 10 μm or less.

  The base sheet may be subjected to a surface treatment in order to improve adhesion with an adjacent layer. As the surface treatment, known resin surface modification techniques such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, and grafting treatment are applied. can do. Only one type of the surface treatment may be applied, or two or more types may be applied.

  Furthermore, it is also possible to apply and form an adhesive layer on the base sheet as an adhesive treatment of the base sheet. An adhesion layer can be formed from the following organic materials and inorganic materials, for example. Examples of the organic material include polyester resins, polyacrylate resins, polyvinyl acetate resins, polyurethane resins, styrene acrylate resins, polyacrylamide resins, polyamide resins, polyether resins, polystyrene resins, Examples thereof include polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyvinyl pyrrolidone and vinyl resins such as modified products thereof, and polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral. Examples of the inorganic material include silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspicion bakumaite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, oxidation Examples thereof include ultrafine particles of colloidal inorganic pigments such as magnesium and titanium oxide.

  Moreover, when manufacturing a plastic film by extending | stretching as said surface treatment, a primer liquid can be apply | coated to an unstretched film and it can also carry out by extending | stretching after that (primer process).

Thermal transfer color material layer The thermal transfer ink sheet used in the present invention has three color thermal transfer color material layers, specifically a magenta color material layer, a yellow color material layer, and a cyan color on one surface of a base sheet. The material layers are preferably provided in the surface order. When the thermal transfer ink sheet is a sublimation type thermal transfer ink sheet, a layer containing a sublimation dye is formed as the thermal transfer color material layer.

In the present invention, the yellow color material layer contains a dye represented by the general formula (I), and the cyan color material layer contains a dye represented by the general formula (VI). In the present invention, the magenta color material layer preferably contains at least one dye selected from the group consisting of dyes represented by the general formula (IV) and the general formula (X). Hereinafter, the dyes contained in the yellow color material layer, the magenta color material layer, and the cyan color material layer will be described.

（一般式（Ｉ）中、環Ａは、任意の置換基を有していても良いアリール基を表し、Ｒ^１およびＲ^２はそれぞれ独立に、水素原子、置換されていても良いアルキル基、置換されていても良いアリル基、置換されていても良いアリール基、または、置換されていても良いシクロアルキル基を表し、Ｒ^３は、置換されていても良いアルキル基、置換されていても良いアルコキシ基、置換されていても良いアミノ基、または水素原子を表し、Ｒ^４は、置換されていても良いアルキル基、または、置換されていても良いアリール基を表す。） Dye for yellow color material layer

(In general formula (I), ring A represents an aryl group which may have an arbitrary substituent, and R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group, Represents an optionally substituted allyl group, an optionally substituted aryl group, or an optionally substituted cycloalkyl group, and R ³ represents an optionally substituted alkyl group, which may be substituted. A good alkoxy group, an optionally substituted amino group, or a hydrogen atom is represented, and R ⁴ represents an optionally substituted alkyl group or an optionally substituted aryl group.)

Among these, the ring A in the general formula (I) is a methyl group-substituted or unsubstituted aryl group, and R ¹ and R ² are each independently a straight chain having 1 to 5 carbon atoms. Or a branched alkyl group which may be substituted, R ³ is a methoxy group, an ethoxy group, or an amino group substituted with a methyl group or an ethyl group, and R ⁴ may be substituted A good aryl group is preferred.

As the dye represented by the general formula (I), specifically, the following dyes are preferable.

（一般式（ＩＶ）中、Ｒ^１６およびＲ^１７はそれぞれ独立に、水素原子、置換されていても良いアルキル基、置換されていても良いアリル基、アルケニル基、またはアラルキル基を表し、Ｒ^１８は、水素原子、メチル基、メトキシ基、またはハロゲン原子を表し、Ｒ^１９は、水素原子、メチル基、メトキシ基、ホルミルアミノ基、アルキルカルボニルアミノ基、アルキルスルホニルアミノ基、またはアルコキシカルボニルアミノ基を表し、Ｒ^２０は、水素原子、置換されていても良いアルキル基、アリル基、プロパルギル基、または置換されていても良いアリール基を表す。） Dye for magenta color material layer

(In the general formula (IV), in each of R ¹⁶ and R ¹⁷ independently represent a hydrogen atom, an optionally substituted alkyl group, an allyl group which may be substituted, an alkenyl group or an aralkyl group,, R ¹⁸ Represents a hydrogen atom, a methyl group, a methoxy group, or a halogen atom, and R ¹⁹ represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an alkylcarbonylamino group, an alkylsulfonylamino group, or an alkoxycarbonylamino group. R ²⁰ represents a hydrogen atom, an optionally substituted alkyl group, an allyl group, a propargyl group, or an optionally substituted aryl group.)

Among these, R ¹⁶ and R ¹⁷ in the general formula (IV) are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and R ¹⁸ is It is preferably a hydrogen atom, R ¹⁹ is an alkylcarbonylamino group, and R ²⁰ is an optionally substituted alkyl group, an allyl group, or a propargyl group having 1 to 4 carbon atoms.

As the dye represented by the general formula (IV), specifically, the following dyes are preferable.

（一般式（Ｘ）中、Ｒ^７１およびＲ^７２はそれぞれ独立に、水素原子、置換されていても良いアルキル基、アリル基、置換されていても良いアリール基、または置換されていても良いシクロアルキル基を表し、Ｒ^７３は、水素原子、炭素数１以上４以下のアルコキシ基、メチル基、またはハロゲン原子を表し、Ｒ^７４は、メチル基、メトキシ基、ホルミルアミノ基、炭素数１以上４以下のアルキルカルボニルアミノ基、炭素数１以上８以下のアルキルスルホニルアミノ基、または炭素数１以上８以下のアルコキシカルボニルアミノ基を表し、Ｒ^７５は、水素原子、ニトロ基、または置換されていても良いアルキル基を表す。）

(In the general formula (X), R ⁷¹ and R ⁷² are each independently a hydrogen atom, an optionally substituted alkyl group, an allyl group, an optionally substituted aryl group, or an optionally substituted cyclo group. R ⁷³ represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a methyl group, or a halogen atom, and R ⁷⁴ represents a methyl group, a methoxy group, a formylamino group, or 1 to 4 carbon atoms. Represents the following alkylcarbonylamino group, an alkylsulfonylamino group having 1 to 8 carbon atoms, or an alkoxycarbonylamino group having 1 to 8 carbon atoms, and R ⁷⁵ may be a hydrogen atom, a nitro group, or a substituted one. Represents a good alkyl group.)

Among these, R ⁷¹ and R ^{72 in} the general formula (X) are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, and R ⁷³ is hydrogen. An atom, R ⁷⁴ is an alkylsulfonylamino group having 1 to 8 carbon atoms, and R ⁷⁵ is a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted. Preferably there is.

As the dye represented by the general formula (X), specifically, the following dyes are preferable.

（一般式（ＶＩＩ）中、Ｘは、−Ｓ−、−Ｏ−、または−ＳＯ_２−を表し、Ｒ^２９は、置換されていても良いアルキル基、置換されていても良いシクロアルキル基、置換されていても良いアリール基または置換されていても良いアリル基を表す。） In the present invention, the magenta color material layer may further contain at least one dye selected from the group consisting of dyes represented by general formula (VII) and general formula (VIII).

(In General Formula (VII), X represents —S—, —O—, or —SO ₂ —, and R ²⁹ represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, Represents an aryl group which may be substituted or an allyl group which may be substituted.)

Among these, it is preferable that X in the general formula (VII) is —O—, and R ²⁹ is an optionally substituted aryl group.

（一般式（ＶＩＩＩ）中、ＸおよびＹはそれぞれ独立に、−Ｓ−、−Ｏ−、または−ＳＯ_２−を表し、Ｒ^３０およびＲ^３１はそれぞれ独立に、置換されていても良いアルキル基、置換されていても良いシクロアルキル基、置換されていても良いアリール基または置換されていても良いアリル基を表す。）

(In the general formula (VIII), X and Y are each independently -S -, - O-, or -SO ₂ - ^represent, respectively ^{R 30} and ^{R 31} are independently optionally substituted alkyl group Represents an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted allyl group.)

Among these, X and Y in the general formula (VIII) are each independently —O—, and R ³⁰ and R ³¹ are each independently an optionally substituted aryl group.

Specifically, as the dye represented by the general formula (VII) or the general formula (VIII), the following dyes are preferable.

（一般式（ＶＩ）中、環Ａは、置換されていても良いアリール基を表し、Ｒ^２７およびＲ^２８はそれぞれ独立に、水素原子、置換されていても良いアルキル基、アリル基、置換されていても良いアリール基、または置換されていても良いシクロアルキル基を表す。） Cyan dye layer dye

(In general formula (VI), ring A represents an aryl group which may be substituted, and R ²⁷ and R ²⁸ each independently represents a hydrogen atom, an alkyl group which may be substituted, an allyl group, or a substituted group. Represents an optionally substituted aryl group or an optionally substituted cycloalkyl group.)

Among these, the ring A in the general formula (VI) is an aryl group substituted with a methyl group, and R ²⁷ and R ²⁸ are each independently a linear or branched chain having 1 to 8 carbon atoms. It is preferably an alkyl group that may have a substituent.

Specifically, the following dyes are preferable as the dye represented by the general formula (VI).

（一般式（ＩＸ）中、Ｒ^３２およびＲ^３３はそれぞれ独立に、置換されていても良いアルキル基、置換されていても良いシクロアルキル基、置換されていても良いアリール基、置換されていても良い複素環基、置換されていても良いアリル基、または置換されていても良いアラルキル基を表わす。） In the present invention, the cyan color material layer may further contain at least one dye selected from the group consisting of dyes represented by the general formula (IX) and the general formula (XI).

(In the general formula (IX), R ³² and R ³³ are each independently an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituted Or a heterocyclic group which may be substituted, an allyl group which may be substituted, or an aralkyl group which may be substituted.

Among these, R ³² and R ³³ in the general formula (IX) each independently have an optionally substituted aryl group, or a linear or branched substituent having 1 to 4 carbon atoms. An alkyl group that may be present is preferred.

Specifically, the following dyes are preferable as the dye represented by the general formula (IX).

（一般式（ＸＩ）中、Ｒ^３４は、置換されていても良いアリール基、または水素原子を表す。）

(In the general formula (XI), R ³⁴ represents an optionally substituted aryl group or a hydrogen atom.)

Among these, R ³⁴ is preferably an aryl group substituted with a hydroxyl group or a hydrogen atom.

Specifically, the following dyes are preferred as the dye represented by the general formula (XI).

  As a material for the heat transferable color material layer, conventionally known dyes can be further blended in addition to the above dyes. For example, those having good characteristics as a printing material, for example, those having a sufficient coloring density and not discolored by light, heat, temperature, etc. are preferred. Diarylmethane dyes, triarylmethane dyes, thiazole dyes Azo dyes such as merocyanine dyes, pyrazolone dyes, methine dyes, acetophenone azomethine, imidazolazomethine, imidazoazomethine, pyridone azomethine, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, Thiazine dyes, azine dyes, acridine dyes, pyridone azo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, thiadiazole azo, triazole azo, disazo azo dyes, spiropyran dyes, indolino Piropiran dyes, fluoran dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone dyes. In the present invention, a dye contained in a commercially available ink ribbon for a sublimation type thermal transfer system can also be used.

  Examples of the binder resin for supporting the dye include cellulose resins such as ethyl cellulose resin, hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, and cellulose acetate resin, polyvinyl alcohol resin, polyvinyl acetate resin, and polyvinyl butyral resin. And vinyl resins such as polyvinyl acetal resin and polyvinyl pyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, and polyester resins. Among these, cellulose-based, vinyl-based, acrylic-based, polyurethane-based, and polyester-based resins are preferable from the viewpoints of heat resistance, dye transferability, and the like.

  The heat transferable color material layer may contain additives such as inorganic fine particles and organic fine particles. Examples of the inorganic fine particles include carbon black, silica, molybdenum disulfide, and the like, and examples of the organic fine particles include polyethylene wax. Further, the heat transferable color material layer may contain a release agent such as silicone, silicone oil, and phosphate ester.

  Examples of the method for forming the heat transferable color material layer include the following methods. For the heat-transferable colorant layer obtained by adding additives such as a release agent to the above dyes and binder resin, if necessary, dissolved in an appropriate organic solvent such as toluene or methyl ethyl ketone, or dispersed in water. A coating solution (dissolved solution or dispersion) is applied to one surface of a substrate sheet by, for example, a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater, etc., and dried. Can be formed. The heat transferable color material layer has a thickness of about 0.2 μm or more and 5.0 μm or less, and the content of the sublimable dye in the heat transferable color material layer is 5 mass% or more and 90 mass% or less, preferably 5 It is preferable that they are mass% or more and 70 mass% or less.

The color material primer layer thermal transfer ink sheet may further include a color material primer layer between the base material sheet and each color material layer. By providing a color material primer layer, not only can the printing density and light resistance be improved, but also the adhesion between the base material and the color material layer is improved, and abnormal transfer of the color material layer to the thermal transfer image receiving sheet during thermal transfer. Can be prevented. The color material primer layer preferably contains the following resin and inorganic fine particles. Moreover, you may mix | blend conventionally well-known various additives.

  As the resin for forming the color material primer layer, polyester resin, polyvinyl pyrrolidone resin, polyvinyl alcohol resin, hydroxyethyl cellulose, polyacrylate resin, polyvinyl acetate resin, polyurethane resin, styrene acrylate resin, polyacrylamide Resins, polyamide resins, polyether resins, polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl acetal resins such as polyvinyl acetoacetal and polyvinyl butyral, and the like.

  The color material primer layer may contain inorganic fine particles, for example, colloidal inorganic pigment ultrafine particles. This prevents dye transfer from the color material layer to the color material primer layer during image formation, and enables effective dye diffusion to the receiving layer side of the thermal transfer image receiving sheet, thereby increasing the print density.

  Conventionally known compounds can be used as the inorganic fine particles. For example, silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate, suspect boehmite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, oxidation Examples include titanium. In particular, colloidal silica and alumina sol are preferably used. These colloidal inorganic pigment ultrafine particles are preferably used with an average primary particle size of 100 nm or less, preferably 50 nm or less.

  Examples of the method for forming the color material primer layer include the following methods. Additives such as mold release agents, if necessary, to the above dyes and binder resin, dissolve in an appropriate organic solvent such as toluene or methyl ethyl ketone, or disperse in water, and the resulting coating for the colorant primer layer The liquid (dissolved liquid or dispersion) is applied to one surface of the substrate sheet by, for example, a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater or the like, and dried. Can be formed. The color material primer layer has a thickness of about 0.2 μm to 5.0 μm.

Protective layer The thermal transfer ink sheet used in the present invention may be provided with a protective layer in the surface order on the same side as the thermal transferable color material layer. After the color material is transferred to the thermal transfer image-receiving sheet, the protective layer is transferred to cover the image, whereby the image can be protected from light, gas, liquid, abrasion and the like. Moreover, you may provide other layers, such as an adhesive layer, a peeling layer, or a mold release layer.

Heat-resistant slip layer The heat-resistant slip layer is mainly composed of a heat-resistant resin. The heat resistant resin is not particularly limited. For example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyether resin, polybutadiene resin, styrene-butadiene copolymer resin, Acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetate propionate resin, cellulose acetate butyrate resin, cellulose acetate-hydrodiene Cellulosic resins such as phthalate resin and cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamideimide resin, poly Boneto resins, and chlorinated polyolefin resins. In particular, the heat resistant resin is preferably at least one selected from the group consisting of polyvinyl butyral resin, polyvinyl acetoacetal resin, acrylic polyol, and cellulose resin.

  The heat resistant slipping layer may be formed by blending additives such as a slipperiness imparting agent, a crosslinking agent, a release agent, an organic powder, and an inorganic powder in addition to the above heat resistant resin.

  In general, the heat-resistant slipping layer is prepared by adding the above-mentioned heat-resistant resin and the above-mentioned slipperiness-imparting agent and additives that are optionally added to the solvent, and dissolving or dispersing each component to form a heat-resistant slipping layer coating solution. After the preparation, the heat resistant slipping layer coating solution can be applied on a substrate and dried. As the solvent in the heat resistant slipping layer coating solution, the same solvents as those in the dye ink can be used.

Examples of the coating method of the heat resistant slipping layer coating liquid include wire bar coating, gravure printing, screen printing, reverse roll coating using a gravure plate, and gravure coating is particularly preferable. The heat resistant slipping layer coating solution may be applied so that the dry coating amount is preferably 0.1 g / m ² or more and 3 g / m ² or less, more preferably 1.5 g / m ² or less.

Set of Thermal Transfer Ink Sheet and Thermal Transfer Image Receiving Sheet The thermal transfer ink sheet and thermal transfer image receiving sheet set according to the present invention is such that the color material layer surface of the thermal transfer ink sheet and the receiving layer surface of the thermal transfer image receiving sheet are overlapped, and the color material layer is placed on the receiving layer. It is used for thermal transfer to form an image on a thermal transfer image receiving sheet. A set of a thermal transfer ink sheet comprising a thermal transferable colorant layer containing a specific dye and a thermal transfer image receiving sheet having a specific layer structure can provide a sufficient print density and suppress catalytic fading. The light resistance of the printed matter can be improved.

Image Forming Method An image forming method according to the present invention comprises:
Preparing a thermal transfer ink sheet comprising a yellow color material layer, a magenta color material layer, and a cyan color material layer on a base material sheet;
Preparing a thermal transfer image-receiving sheet comprising a particle-containing layer and a receiving layer in order on a substrate;
Superposing the color material layer surface of the thermal transfer ink sheet and the receptor layer surface of the thermal transfer image receiving sheet, thermally transferring the color material layer onto the receptor layer, and forming an image on the thermal transfer image receiving sheet;
Comprising
The yellow color material layer comprises a dye represented by the general formula (I), and the cyan color material layer comprises a dye represented by the general formula (VI);
The particle-containing layer comprises hollow particles and / or microballoons. According to the image forming method of the present invention, a sufficient print density can be obtained, and the light fastness of the printed matter can be improved by suppressing the catalytic fading. The thermal transfer ink sheet and the thermal transfer image receiving sheet are as described above.

  In the image forming method according to the present invention, in the step of thermally transferring the color material layer onto the receiving layer, the yellow color material layer, the magenta color material layer, the cyan color material layer, It is preferable to perform thermal transfer in the order of the magenta color material layer. By performing thermal transfer in this order, the yellow color material to be printed in the first color penetrates (diffuses) under the image receiving paper with the print heat, and the distance between the yellow color material and the magenta color material or the yellow color material and the cyan color material. By separating the materials, the light fading of the printed matter can be further improved by further suppressing the catalytic fading.

  In the image forming method according to the present invention, the printing speed is preferably 0.1 ms / line or more and 5.0 ms / line or less (300 dpi conversion), more preferably 0.2 ms / line or more and 2.0 ms / line or less (300 dpi). Conversion). By increasing the printing speed, catalytic fading can be further suppressed and the light resistance of the printed matter can be further improved.

  As a thermal transfer recording apparatus that can be used in such an image forming method, a known apparatus can be used and is not particularly limited. In the present invention, a commercially available thermal transfer recording apparatus can be used, and examples include a sublimation thermal transfer printer (manufactured by ALTECH ADS, model: MEGAPIXEL III).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

Example 1
Using RC paper (manufactured by Mitsubishi Paper Industries Co., Ltd.) as the base material for producing the thermal transfer image-receiving sheet 1, the particle-containing layer coating solution 1 and the receiving layer coating solution 1 having the following composition were heated to 40 ° C., respectively. using the coating amount after drying respectively 10.0 g ^/ m 2, and simultaneously coated so that 3.0 g / ^{m 2,} was cooled for 30 seconds at 5 ° C., then dried for 2 minutes at 50 ° C. Thermal transfer image-receiving sheet 1 (layer constitution: substrate / particle-containing layer / receiving layer) was obtained. The coating speed was 20 m / min. This thermal transfer image-receiving sheet had a layer structure as shown in FIG.
Composition of coating liquid 1 for particle-containing layer : hollow particles (volume average particle size: 0.5 μm, average hollowness: 45%, manufactured by Rohm and Haas Co., Ltd., trade name: Ropeke ST) 59 parts by mass, gelatin (new Ta Gelatin Co., Ltd., trade name: N1236) 28 parts by mass binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B-13) 5 parts by mass binder resin (styrene)・ Acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 8 parts by mass
Composition of coating liquid 1 for receiving layer : Binder resin (vinyl chloride emulsion: vinyl chloride / vinyl acetate = 97.5 / 2.5, Tg = 83 ° C.) 100 parts by mass / urethane associative thickener (viscosity: 2000 , Viscosity ratio: 3.0, manufactured by ADEKA Corporation, trade name: UH-526) 3.8 parts by weight, aqueous dispersion of release agent (silicone dispersion) 10 parts by weight, epoxy cross-linking agent (Nagase ChemteX) (Product name: Denacol EX512)
5 parts by mass / surfactant (dioctylsulfosuccinic acid Na salt, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.5 parts by mass The coating solution for the receiving layer is an aqueous dispersion in which the above components are dispersed in water by a known method. It is a coating solution.

Preparation of a vinyl chloride-based emulsion In a 2.5 L autoclave, 600 g of deionized water, 438.8 g of vinyl chloride monomer (97.5% by mass with respect to all charged monomers) and 11.2 g of vinyl acetate (all charged) A monomer mixture of 2.5% by mass with respect to the monomer, 2.25 g of potassium persulfate was charged. The reaction mixture was stirred with a stirring blade so as to maintain a rotation speed of 120 rpm, and the temperature of the reaction mixture was raised to 60 ° C. to initiate polymerization. 180 g of a 5% by mass aqueous sodium dodecylbenzenesulfonate solution (2% by mass with respect to all charged monomers) was continuously added until after the start of polymerization until 4 hours, and the saturated vapor pressure of the vinyl chloride monomer at a polymerization pressure of 60 ° C. Then, the polymerization was stopped when the pressure dropped from 0.6 MPa, and the remaining monomer was recovered to obtain a vinyl acetate emulsion.

Preparation of aqueous dispersion of release agent 85 g of ethyl acetate, 16 g of epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-22-3000T) and aralkyl-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name X) -24-510) 8 g was dissolved. Next, 14 g of sodium triisopropyl naphthalene sulfonate (solid content: 10%) was dissolved in 110 g of pure water. The two liquids were mixed and stirred, and then dispersed using a homogenizer to prepare a dispersion. Thereafter, ethyl acetate was removed under reduced pressure while heating the dispersion to 30 to 60 ° C. to obtain an aqueous dispersion of silicone.

Preparation of Thermal Transfer Ink Sheet 1 A polyethylene terephthalate film having a thickness of 5 μm is used as a base sheet, and a heat resistant slipping layer coating liquid 1 having the following composition is formed thereon by gravure coating to give 0.5 g / m ² when dried. Thus, it was applied and dried to form a heat resistant slipping layer.
Composition of coating solution 1 for heat-resistant slipping layer / polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
60.8 parts by mass polyisocyanate curing agent (Bernock D750, manufactured by Dainippon Ink & Chemicals, Inc.)
4.2 parts by mass-Zinc stearyl phosphate (LBT1830 purification, manufactured by Sakai Chemical Industry Co., Ltd.) 10 parts by mass, zinc stearate (SZ-PF, manufactured by Sakai Chemical Industry Co., Ltd.) 10 parts by mass, polyethylene wax (Polywax 3000 Toyo Adress 3 parts by mass / ethoxylated alcohol-modified wax (Unitox 750, manufactured by Toyo Adre Co., Ltd.)
7 parts by mass • 200 parts by mass of methyl ethyl ketone (MEK) • 100 parts by mass of toluene

Next, the colorant primer layer coating solution 1 having the following composition was applied to the other side of the base sheet on which the heat-resistant slip layer was provided, and dried at 0.6 g / m ² when dried. Thus, a color material primer layer was provided. Subsequently, a yellow color material layer coating liquid 1, a magenta color material layer coating liquid 1 and a cyan color material layer coating liquid 1 having the following composition are dried on the color material primer layer at a rate of 0.6 g / m ^2. In this order, the thermal transfer ink sheet 1 (layer structure: heat-resistant slip property) is formed by repeatedly coating and drying in this order and forming a yellow color material layer, a magenta color material layer, and a cyan color material layer. Layer / base material sheet / color material primer layer / thermal transferable color material layer). This thermal transfer ink sheet had a layer structure as shown in FIG.
Colorant primer layer coating solution 1
-Polyvinylpyrrolidone resin (trade name: K-90, manufactured by ISP) 3 parts by mass-Alumina sol (average primary particle size 10 x 100 nm, solid content 10%, manufactured by Nissan Chemical Industries, Ltd., trade name: Alumina sol 200) 30 parts by mass / water 50 parts by mass / IPA (isopropyl alcohol) 17 parts by mass

Composition of coating solution 1 for yellow color material layer -Yellow dye (chemical formula: I-2) 2.6 parts by mass-Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass
Composition of coating liquid 1 for magenta color material layer -magenta dye (chemical formula: IV-2) 3.0 parts by mass-binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass
Composition of Cyan Color Material Layer Coating Solution 1 / Cyan Dye (Chemical Formula: VI-1) 3.8 parts by mass Binder Resin (Polyvinyl Acetal Resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass

  Thus, a set of the thermal transfer image receiving sheet 1 and the thermal transfer ink sheet 1 was obtained. An image was formed using this set, and the following evaluation was performed.

Example 2
Production of Thermal Transfer Ink Sheet 2 A thermal transfer ink sheet 2 was produced in the same manner as in Example 1 except that the composition of the magenta color material layer coating solution was changed as follows.

Composition of coating liquid 2 for magenta color material layer -Magenta dye (chemical formula: X-3) 3.0 parts by mass-Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 47.0 parts by mass, toluene 47.0 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 1 and the thermal transfer ink sheet 2 and the following evaluation was performed.

Example 3
Production of Thermal Transfer Ink Sheet 3 A thermal transfer ink sheet 3 was produced in the same manner as in Example 1 except that the composition of the magenta color material layer coating solution was changed as follows.

Composition of Coating Solution 3 for Magenta Color Material Layer -Magenta Dye (Chemical Formula: IV-2) 2.1 parts by mass-Magenta Dye (Chemical Formula: VIII-1) 2.1 parts by mass-Binder resin (polyvinyl acetal resin, KS- 5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 1 and the thermal transfer ink sheet 3 and evaluated as follows.

Example 4
Production of Thermal Transfer Ink Sheet 4 A thermal transfer ink sheet 4 was produced in the same manner as in Example 1 except that the composition of the coating solution for cyan color material layer was as follows.

Composition of coating liquid 2 for cyan color material layer : Cyan dye (chemical formula: VI-1) 2.6 parts by mass Cyan dye (chemical formula: IX-1) 2.6 parts by mass Binder resin (polyvinyl acetal resin, KS- 5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 1 and the thermal transfer ink sheet 4 and evaluated as follows.

Example 5
Preparation of thermal transfer image-receiving sheet 2 A thermal transfer image-receiving sheet 2 was prepared in the same manner as in Example 1 except that the composition of the coating solution for the particle-containing layer was as follows.
Composition of coating liquid 2 for particle-containing layer : 59 parts by mass of microballoon (manufactured by Matsumoto Yushi Co., Ltd., trade name: FN-80GS), 28 parts by mass of gelatin (manufactured by Nitta Gelatin Co., Ltd., trade name: N1236) Binder resin (styrene / acrylic resin, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B-13) 5 parts by mass / binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: John Krill 62J) 8 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 2 and the thermal transfer ink sheet 1, and the following evaluation was performed.

Comparative Example 1
Preparation of thermal transfer image-receiving sheet 3 A thermal transfer image-receiving sheet 3 was prepared in the same manner as in Example 1 except that the following particle-free coating solution was used instead of the particle-containing layer coating solution.
Composition of particle-free coating solution Gelatin (Nitta Gelatin Co., Ltd., trade name: N1236) 87 parts by mass Binder resin (styrene / acrylic resin, Shin-Nakamura Chemical Co., Ltd., trade name: New Coat B -13) 5 parts by mass Binder resin (styrene / acrylic resin, manufactured by BASF Japan Ltd., trade name: Jonkrill 62J) 8 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 1, and the following evaluation was performed.

Comparative Example 2
An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 2, and the following evaluation was performed.

Comparative Example 3
An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 3 and evaluated as follows.

・バインダー樹脂（ポリビニルアセタール樹脂、ＫＳ−５、積水化学工業（株）製）
３．０質量部
・ポリエチレンワックス ０．１質量部
・メチルエチルケトン ４６．６質量部
・トルエン ４６．６質量部 Comparative Example 4
Production of Thermal Transfer Ink Sheet 5 A thermal transfer ink sheet 5 was produced in the same manner as in Example 1 except that the composition of the magenta color material layer coating solution and the cyan color material layer coating solution were as follows.
Composition of coating solution 4 for magenta color material layer : magenta dye (chemical formula: IV-4) 3.0 parts by mass binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass
Composition of coating solution 3 for cyan color material layer, cyan dye represented by the following chemical formula 3.8 parts by mass

・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 46.6 parts by mass, toluene 46.6 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 5, and the following evaluation was performed.

・バインダー樹脂（ポリビニルアセタール樹脂、ＫＳ−５、積水化学工業（株）製）
３．０質量部
・ポリエチレンワックス ０．１質量部
・メチルエチルケトン ４６．６質量部
・トルエン ４６．６質量部 Comparative Example 5
Production of Thermal Transfer Ink Sheet 6 A thermal transfer ink sheet 6 was produced in the same manner as in Example 1 except that the composition of the coating solution for the cyan color material layer was changed as follows.
Composition of Cyan Color Material Layer Coating Solution 4 Cyan Dye Shown by the Chemical Formula below 3.8 parts by mass

・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 46.6 parts by mass, toluene 46.6 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 6 and evaluated as follows.

・バインダー樹脂（ポリビニルアセタール樹脂、ＫＳ−５、積水化学工業（株）製）
３．０質量部
・ポリエチレンワックス ０．１質量部
・メチルエチルケトン ４５．０質量部
・トルエン ４５．０質量部 Comparative Example 6
Preparation of Thermal Transfer Ink Sheet 7 A thermal transfer ink sheet 7 was prepared in the same manner as in Example 1 except that the composition of the yellow color material layer coating solution was as follows.
Composition of coating solution 2 for yellow color material layer 2.6 parts by mass of a yellow dye represented by the following chemical formula

・ Binder resin (polyvinyl acetal resin, KS-5, manufactured by Sekisui Chemical Co., Ltd.)
3.0 parts by mass, polyethylene wax 0.1 parts by mass, methyl ethyl ketone 45.0 parts by mass, toluene 45.0 parts by mass

  An image was formed using the set of the thermal transfer image receiving sheet 3 and the thermal transfer ink sheet 7, and the following evaluation was performed.

Evaluation of Printed Material Using the set of the thermal transfer image receiving sheet and the thermal transfer ink sheet prepared as described above, (1) evaluation of printing density, (2) evaluation of storage stability, and (3) evaluation of light resistance were performed. In the evaluation, the yellow, magenta, and cyan panels of the genuine ink ribbon of the sublimation type thermal transfer printer (manufactured by DNP Photolcio, model: DS40) were cut out, and each of the thermal transfer ink sheets prepared above was yellow. , Magenta, and cyan panels were used as thermal transfer ink sheets.

(1) Print density evaluation Using the set of the thermal transfer image-receiving sheet and thermal transfer ink sheet prepared above and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40), the RGB value is 15 × n (n = 0) To 17) are printed, and a value at which the optical reflection density is maximized by an optical densitometer ((spectrolino manufactured by Gretag Macbeth) (Ansi-A, D65)) is measured, and black (yellow, magenta) is measured. , The OD value (optical density) of the image obtained by superimposing three colors of cyan.
Evaluation criteria A : The maximum density is 107% or more compared with the OD value of Comparative Example 1. B: The maximum density is 103% or more and less than 107% compared with the OD value of Comparative Example 1. Compared to the OD value, the maximum concentration is 95% or more and less than 103%. X: Compared with the OD value of Comparative Example 1, the maximum concentration is less than 95%.

(2) Storage stability evaluation After the thermal transfer ink sheet prepared above was stored in a small volume and stored in a high temperature and high humidity environment (40 ° C. and 90% RH) for one week, the surface of the thermal transfer ink sheet was traced with a finger. The storage stability was evaluated according to the following evaluation criteria.
-Evaluation criteria ( circle): Dye did not adhere to the finger which traced the surface.
X: The dye adhered to the finger tracing the surface.

(3) Light resistance evaluation Using the set of the thermal transfer image-receiving sheet and thermal transfer ink sheet prepared above and a sublimation thermal transfer printer (manufactured by DNP Photolcio, model: DS40), the RGB value is 15 × n (n = 0) To 17) were printed, and the light resistance was evaluated with a xenon fade meter under the following conditions.
(I) Conditions for light resistance evaluation / irradiation tester: Ci4000 manufactured by Atlas
・ Light source: Xenon lamp ・ Filter: Inside = CIRA
Outside = soda lime black panel temperature: 45 (° C)
Irradiation intensity: 1.2 (W / m ² ) ... Measured value at 420 (nm) Irradiation energy: 400 (kJ / m ² ) ... Integrated value at 420 (nm) (ii) Light resistance Next, the change in the optical reflection density before and after the irradiation under the above light resistance conditions was measured with an optical densitometer (manufactured by Gretag Macbeth, spectrolino), and the optical reflection density before the irradiation was about 1.0 step. The concentration residual ratio was calculated by the following formula.
Concentration residual ratio = (optical density after irradiation) / (optical density before irradiation) × 100
Evaluation criteria A : Concentration residual ratio is 110% or more with reference to the concentration residual ratio of Comparative Example 1 ○: Concentration residual ratio is higher than 105% and lower than 110% based on the concentration residual ratio of Comparative Example 1 ×: Comparison Based on the residual concentration rate of Example 1, the residual concentration rate is 105% or less

The results of the above evaluations are shown in Table 1. The set of the thermal transfer image receiving sheet and the thermal transfer ink sheet of the example satisfying the composition of the present invention of the present invention can obtain a sufficient print density as compared with the set of the thermal transfer image receiving sheet and the thermal transfer ink sheet of the comparative example, It can also be seen that the light fastness of the printed material can be improved by suppressing the catalytic fading.

DESCRIPTION OF SYMBOLS 10 Thermal transfer image receiving sheet 11 Base material 12 Particle-containing layer 13 Receiving layer 20 Thermal transfer ink sheet 21 Base material sheet 22 Color material primer layer 23 Thermal transfer color material layer 24 Yellow color material layer 25 Magenta color material layer 26 Cyan color material layer 27 Heat resistance Slippery layer

Claims (7)

A set of a thermal transfer ink sheet comprising a yellow color material layer, a magenta color material layer, and a cyan color material layer on a substrate sheet, and a thermal transfer image receiving sheet comprising a particle-containing layer and a receiving layer on the substrate. There,
The yellow color material layer comprises a dye represented by the general formula (I), and the cyan color material layer comprises a dye represented by the general formula (VI);
A set of a thermal transfer ink sheet and a thermal transfer image receiving sheet, wherein the particle-containing layer comprises hollow particles and / or microballoons.

(In general formula (I), ring A represents an aryl group which may have an arbitrary substituent, and R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group, Represents an optionally substituted allyl group, an optionally substituted aryl group, or an optionally substituted cycloalkyl group, and R ³ represents an optionally substituted alkyl group, which may be substituted. A good alkoxy group, an optionally substituted amino group, or a hydrogen atom is represented, and R ⁴ represents an optionally substituted alkyl group or an optionally substituted aryl group.)

(In general formula (VI), ring A represents an aryl group which may be substituted, and R ²⁷ and R ²⁸ each independently represents a hydrogen atom, an alkyl group which may be substituted, an allyl group, or a substituted group. Represents an optionally substituted aryl group or an optionally substituted cycloalkyl group.) Ring A in the general formula (I) is a methyl group-substituted or unsubstituted aryl group, and R ¹ and R ² are each independently a linear or branched group having 1 to 5 carbon atoms A chain-like optionally substituted alkyl group, R ³ is a methoxy group, an ethoxy group, or an amino group substituted with a methyl group or an ethyl group, and R ⁴ is an optionally substituted aryl group Group,
Ring A in the general formula (VI) is an aryl group substituted with a methyl group, and R27 and R28 each independently have a linear or branched substituent having 1 to 8 carbon atoms. The set of a thermal transfer ink sheet and a thermal transfer image receiving sheet according to claim 1, wherein the set is an alkyl group which may be used. The thermal transfer ink according to claim 1 or 2, wherein the magenta color material layer comprises at least one dye selected from the group consisting of dyes represented by general formula (IV) and general formula (X). Sheet and thermal transfer image-receiving sheet set.

(In the general formula (IV), in each of R ¹⁶ and R ¹⁷ independently represent a hydrogen atom, an optionally substituted alkyl group, an allyl group which may be substituted, an alkenyl group or an aralkyl group,, R ¹⁸ Represents a hydrogen atom, a methyl group, a methoxy group, or a halogen atom, and R ¹⁹ represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an alkylcarbonylamino group, an alkylsulfonylamino group, or an alkoxycarbonylamino group. R ²⁰ represents a hydrogen atom, an optionally substituted alkyl group, an allyl group, a propargyl group, or an optionally substituted aryl group.)

(In the general formula (X), R ⁷¹ and R ⁷² are each independently a hydrogen atom, an optionally substituted alkyl group, an allyl group, an optionally substituted aryl group, or an optionally substituted cyclo group. R ⁷³ represents a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a methyl group, or a halogen atom, and R ⁷⁴ represents a methyl group, a methoxy group, a formylamino group, or 1 to 4 carbon atoms. Represents the following alkylcarbonylamino group, an alkylsulfonylamino group having 1 to 8 carbon atoms, or an alkoxycarbonylamino group having 1 to 8 carbon atoms, and R ⁷⁵ may be a hydrogen atom, a nitro group, or a substituted one. Represents a good alkyl group.) The thermal transfer ink sheet according to claim 3, wherein the magenta color material layer further comprises at least one dye selected from the group consisting of dyes represented by general formula (VII) and general formula (VIII). And a set of thermal transfer image-receiving sheets.

(In General Formula (VII), X represents —S—, —O—, or —SO ₂ —, and R ²⁹ represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, Represents an aryl group which may be substituted or an allyl group which may be substituted.)

(In the general formula (VIII), X and Y are each independently -S -, - O-, or -SO ₂ - ^represent, respectively ^{R 30} and ^{R 31} are independently optionally substituted alkyl group Represents an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted allyl group.) The cyan colorant layer further comprises at least one dye selected from the group consisting of dyes represented by general formula (IX) and general formula (XI). A set of the thermal transfer ink sheet and the thermal transfer image receiving sheet described in the item.

(In the general formula (IX), R ³² and R ³³ are each independently an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or a substituted Or a heterocyclic group which may be substituted, an allyl group which may be substituted, or an aralkyl group which may be substituted.

(In the general formula (XI), R ³⁴ represents an optionally substituted aryl group or a hydrogen atom.)   6. The thermal transfer ink sheet and thermal transfer image receiver according to claim 1, wherein the thermal transfer ink sheet further comprises a color material primer layer between the base material layer and the color material layer of each color. A set of sheets. Preparing a thermal transfer ink sheet comprising a yellow color material layer, a magenta color material layer, and a cyan color material layer on a base material sheet;
Preparing a thermal transfer image-receiving sheet comprising a particle-containing layer and a receiving layer in order on a substrate;
Superposing the color material layer surface of the thermal transfer ink sheet and the receiving layer surface of the thermal transfer image receiving sheet, thermally transferring the color material layer onto the receiving layer, and forming an image on the thermal transfer image receiving sheet;
Comprising
The yellow color material layer comprises a dye represented by the general formula (I), and the cyan color material layer comprises a dye represented by the general formula (VI);
The image forming method, wherein the particle-containing layer comprises hollow particles and / or microballoons.

(In general formula (I), ring A represents an aryl group which may have an arbitrary substituent, and R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group, Represents an optionally substituted allyl group, an optionally substituted aryl group, or an optionally substituted cycloalkyl group, and R ³ represents an optionally substituted alkyl group, which may be substituted. A good alkoxy group, an optionally substituted amino group, or a hydrogen atom is represented, and R ⁴ represents an optionally substituted alkyl group or an optionally substituted aryl group.)

(In general formula (VI), ring A represents an aryl group which may be substituted, and R ²⁷ and R ²⁸ each independently represents a hydrogen atom, an alkyl group which may be substituted, an allyl group, or a substituted group. Represents an optionally substituted aryl group or an optionally substituted cycloalkyl group.)

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