JP2017189913A - Heat transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat transfer recording material good inn transfer sensitivity and having no printing wrinkle, detachment lines, adhesion, abnormal transfer, bleeding nor background dirt.SOLUTION: There is provided a heat transfer recording material consisting of a combination of a heat transfer image receiving sheet by laminating a substrate sheet, a porous layer and a receiving layer in this order, and a heat transfer recording medium having a dye layer on one surface of a substrate and a heat resistant lubricity layer on another surface, the receiving layer contains a vinyl chloride/vinyl acetate copolymer or a vinyl chloride/acryl compound copolymer, the dye layer contains a heat migrating dye, a binder resin and a mold releasing agent, the mold releasing agent consists of a polyether modified silicone oil and a perfluoroalkyl compound with mass ratio of 9:1 to 6:4, and weight ratios of the heat migrating dye to the binder resin are different between a range from outermost surface of the dye layer to depth of 0.1 t and from the depth to 1.0 t.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermal transfer recording material.

  In general, a thermal transfer recording medium is an ink ribbon called a thermal ribbon, which is used in a thermal transfer type printer, and has a thermal transfer layer on one side of the substrate and heat resistance on the other side of the substrate. A slipping layer (back coat layer) is provided. Here, the thermal transfer layer is a layer of ink, and the ink is sublimated (sublimation transfer method) or melted (melt transfer method) by the heat generated in the thermal head of the printer, so that a thermal transfer image receiving sheet (transferred material). Is to be transferred to.

  Currently, among the thermal transfer systems, the sublimation transfer system can easily form full-color images with various functions of the printer, so digital camera self-prints, cards such as identification cards, amusement output, etc. Widely used. Along with the diversification of applications, there is a growing demand for miniaturization, high speed, low cost, and durability of the prints that can be obtained. In recent years, printing has been performed on the same side of the substrate as the surface with the thermal transfer layer. 2. Description of the Related Art Thermal transfer recording media having a plurality of thermal transfer layers provided so as not to overlap a protective layer that imparts durability to an object have become widespread.

  Under such circumstances, along with the diversification and widespread use of applications, there has arisen a problem that sufficient print density cannot be obtained with the conventional thermal transfer recording medium as the printing speed of the printer further increases. In order to increase the transfer sensitivity, attempts have been made to improve the transfer sensitivity in printing by reducing the thickness of the thermal transfer recording medium, but printing wrinkles due to heat, pressure, etc. during the manufacture of the thermal transfer recording medium or during printing have been attempted. Occurs, or in some cases breaks.

  In addition, attempts have been made to increase the printing density and transfer sensitivity in printing by increasing the dye / resin (Dye / Binder) ratio in the dye layer of the thermal transfer recording medium. In addition to being up, a part of the dye migrates to the heat-resistant slipping layer of the thermal transfer recording medium during the winding state in the manufacturing process (setback), and when the rewinding is performed, the migrated dye has another color. When the dye layer or the protective layer is re-transferred (back-in reverse) and the contaminated layer is thermally transferred to the transfer material, a hue different from the designated color or so-called background stain occurs.

  Attempts have also been made to increase the energy at the time of image formation on the printer side rather than on the thermal transfer recording medium side, but not only the power consumption increases, but also the life of the printer thermal head is shortened, and at the time of printing. The dye layer and the transfer target are fused, and a peeling line generated because the dye layer and the transfer target do not peel continuously, or so-called abnormal transfer in which the dye layer is transferred to the transfer target is likely to occur. .

  A method of using a releasing agent such as a silicone compound or a fluorine compound has been proposed for preventing fusion between the dye layer and the transfer target. As one of the methods, a method of introducing these release agents to the transfer target side has been proposed. However, in the recent sublimation type thermal transfer recording method, the scratch resistance, alcohol resistance, light resistance, etc. From the viewpoint of improving protection resistance, a transparent resin is often laminated as a protective layer on the transferred material after printing. At this time, if a release agent is present on the transfer target, the protective layer is hardly transferred, which may be disadvantageous for lamination.

As another method, it is also proposed to introduce a release agent into the dye layer.
For example, in Patent Document 1, in a dye layer ink containing at least a sublimable dye, a binder resin, and a release agent, the binder resin is a polyvinyl acetal resin, and the release agent is a polysiloxane and an acetal resin. A dye layer ink characterized by being a copolymer of the above and a polyether-modified silicone has been proposed.
Patent Document 2 discloses a thermal transfer recording medium containing a fluorosurfactant in the dye layer.

  However, when a thermal transfer recording medium proposed in Patent Documents 1 and 2 is used for printing with a recent high-speed printer using a sublimation transfer method, a sufficient print density cannot be obtained, and a peeling line is generated during thermal transfer. In addition, prints with sufficiently satisfactory quality such as abnormal transfer were not obtained. Also, to prevent peeling lines and abnormal transfer, increasing the amount of release agent added to the dye layer does not lead to resolution of peeling lines or abnormal transfer, but also causes blurring of images, smudges, and ink dyes. As a result, coating problems such as bubbling occurred, and printing wrinkles were generated due to the expansion of the thermal transfer recording medium due to the application of hot pressure. Also, assuming that the cause of printing wrinkles was a decrease in heat resistance of the thermal transfer recording medium due to the release agent in the dye layer, printing was performed with a lower release agent compounding ratio. Also, the thermal transfer recording medium and the thermal transfer image-receiving sheet are stuck.

JP 2007-84670 A JP-A-7-101166

  Therefore, the present invention has an object to provide a thermal transfer recording material that has good transfer sensitivity and does not cause printing wrinkles, peeling lines, thermal transfer recording medium and thermal transfer image-receiving sheet, abnormal transfer, blurring, and soiling. To do.

  The present invention is for solving the above-mentioned problems, and the invention according to claim 1 is a thermal transfer image receiving sheet in which at least a base sheet, a porous layer, and a receiving layer are laminated in this order. A thermal transfer recording material comprising a combination of a thermal transfer recording medium having at least a dye layer on one surface of a substrate and having at least a heat-resistant slipping layer on the other surface of the substrate, the receiving layer Includes a vinyl chloride / vinyl acetate copolymer or a vinyl chloride / acrylic compound copolymer, the dye layer includes a heat transfer dye, a binder resin, and a release agent, and the release agent is a polyether. It consists of a modified silicone oil and a perfluoroalkyl compound, the ratio of the polyether-modified silicone oil and the perfluoroalkyl compound is 9: 1 to 6: 4 by mass ratio, and the thickness of the dye layer is t The weight ratio of the heat transferable dye to the binder resin is different in the range from the outermost surface of the dye layer to a depth of 0.1 t and in the range from 1.0 t to 1.0 t. It is.

In the invention according to claim 2, the weight ratio of the heat transferable dye to the binder resin in the range from the outermost surface of the dye layer to a depth of 0.1 t is a1, and the depth from the outermost surface of the dye layer is 0. 2. The thermal transfer recording according to claim 1, wherein the relationship of the following formula (1) is established when the weight ratio of the heat transfer dye to the binder resin in the range from 1 t to 1.0 t is a2. Material.
1.1 ≦ a2 / a1 ≦ 1.5 (1)

  According to a third aspect of the present invention, in the thermal transfer recording according to the first or second aspect, the content of the release agent is 0.5 to 3.0% by mass with respect to the binder resin. Material.

In the invention according to claim 4, the weight ratio of the release agent to the binder resin in the range from the outermost surface of the dye layer to a depth of 0.1 t is b1, and the depth from the outermost surface of the dye layer is 0. The following formulas (1), (2), and (3) are satisfied when the weight ratio of the release agent to the binder resin in the range from 1 t to 1.0 t is b2. 3. The thermal transfer recording material according to 1 or 2.
b1 ≠ b2 (1)
0.5% by mass ≦ b1 ≦ 4.0% by mass (2)
0% by mass ≦ b2 ≦ 3.0% by mass (3)

  The invention according to claim 5 is the thermal transfer recording material according to any one of claims 1 to 4, wherein the polyether-modified silicone oil has a molecular weight of 8000 or more.

  The thermal transfer recording material according to one aspect of the present invention has good transfer sensitivity, and does not cause printing wrinkles, peeling lines, thermal transfer recording medium and thermal transfer image-receiving sheet, abnormal transfer, blurring, and scumming. Material can be provided.

It is a schematic sectional drawing which shows the structure of the thermal transfer recording medium which concerns on embodiment of this invention. It is a schematic sectional drawing which shows the structure of the thermal transfer image receiving sheet which concerns on embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the present invention. However, it will be apparent that one or more embodiments may be practiced without such specific details. In addition, in order to simplify the drawings, descriptions of well-known structures and devices are omitted.

(Thermal transfer recording material 1)
A thermal transfer recording material 1 according to an embodiment of the present invention includes a thermal transfer recording medium 2 and a thermal transfer image receiving sheet 3.

(Thermal transfer recording medium 2)
As shown in FIG. 1, the heat-sensitive transfer recording medium 2 is provided with a heat-resistant slipping layer 40 that imparts slidability with a thermal head on one surface of the substrate 10, and an undercoat layer on the other surface of the substrate 10. 20 and the dye layer 30 are sequentially formed.

(Substrate 10)
The base material 10 is required to have heat resistance and strength that do not soften and deform due to heat pressure in thermal transfer. Therefore, as the substrate 10, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide, aramid, polystyrene, and other synthetic resin films, and condenser paper, A composite of papers such as paraffin paper alone or in combination can be used. Among these, a polyethylene terephthalate film is preferable in view of physical properties, workability, cost, and the like.

  Moreover, the base material 10 can use the thing in the range whose thickness is 2 micrometers or more and 50 micrometers or less in consideration of operativity and workability. Even within this range, in consideration of handling properties such as transfer suitability and workability, those within the range of 2 μm or more and 9 μm or less are preferable.

  Moreover, it is also possible to perform an adhesion treatment on at least one of the surfaces of the base material 10 on which the heat resistant slipping layer 40 and the undercoat layer 20 are formed. As this adhesion treatment, for example, corona treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, plasma treatment, primer treatment or the like can be applied. Two or more of these treatments can be used in combination. By performing this adhesion treatment, the adhesion of the heat resistant slipping layer 40 and the undercoat layer 20 to the substrate 10 can be enhanced.

(Undercoat layer 20)
The undercoat layer 20 is mainly formed of a binder having good adhesion to both the base material and the dye layer. Examples of the binder include polyvinyl pyrrolidone resins, polyvinyl alcohol resins, polyester resins, polyurethane resins, polyacrylic resins, polyvinyl formal resins, epoxy resins, polyvinyl butyral resins, polyamide resins, and polyethers. Resin, polystyrene resin, styrene-acrylic copolymer resin and the like.

Coating amount after drying of the undercoat layer 20, but are not unconditionally limited, in coating amount of solid content ^is preferably ^{0.02g / m 2 ~2.0g / m 2} . When the film thickness is less than 0.02 g / m ² , the transfer sensitivity is lowered, and when it is thicker than 2.0 g / m ² , the heat transfer from the thermal head to the dye layer is deteriorated, and the print density is reduced. This causes the disadvantage of lowering.
Here, the coating amount after drying the undercoat layer 20 refers to the amount of solid content remaining after coating and drying the coating solution for forming the undercoat layer. Similarly, the coating amount of the other layers described later also refers to the solid content remaining after coating and drying each coating solution.

  For the undercoat layer 20, known additives such as colloidal inorganic pigment ultrafine particles, isocyanate compounds, silane coupling agents, dispersants, viscosity modifiers, stabilizers and the like can be used. As the colloidal inorganic pigment ultrafine particles, conventionally known materials can be used. For example, silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or water thereof) (Japanese, pseudo boehmite, etc.), aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, titanium oxide and the like.

(Dye layer 30)
The dye layer 30 is formed by, for example, preparing a coating solution for forming a dye layer by blending a heat transferable dye, a binder resin, a release agent, a solvent, and the like, and applying and drying the coating solution. An appropriate coating amount of the dye layer 30 after drying is about 1.0 g / m ² . In addition, the dye layer 30 can be composed of a single layer, or a plurality of layers can be repeatedly formed on the same surface of the same base material in the surface order.

  The heat transferable dye contained in the dye layer 30 can be used as long as it is a dye that melts, diffuses or sublimates and transfers by heat, and is not particularly limited. Among these heat transferable dyes, examples of yellow components include Solvent Yellow 56, 16, 30, 93, 33, Disperse Yellow 201, 231, 33, and the like. Examples of the magenta component include C.I. I. Disperse thread 60, C.I. I. Disperse violet 26, C.I. I. Solvent Red 27, or C.I. I. Solvent Red 19 etc. can be mentioned. As the cyan component, for example, C.I. I. Disperse Blue 354, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 36, or C.I. I. Disperse Blue 24 and the like. In general, the ink dye is toned by combining the above-mentioned dyes.

  Examples of the binder resin contained in the dye layer 30 include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, and cellulose acetate, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl. Examples thereof include vinyl resins such as pyrrolidone and polyacrylamide, polyester resins, styrene-acrylonitrile copolymer resins, and phenoxy resins, but are not particularly limited.

  Here, when the film thickness of the dye layer 30 is t, the weight ratio of the heat transferable dye to the binder resin in the range from the outermost surface of the dye layer 30 to the depth of 0.1 t is a1, and the outermost surface of the dye layer 30 It is preferable that 1.1 ≦ a2 / a1 ≦ 1.5 holds when the weight ratio of the heat transferable dye to the binder resin in the depth range from 0.1 to 1.0 t is a2. When a2 / a1 is less than 1.1, the solubility of the dye in the binder is extremely reduced. Therefore, when a thermal transfer recording medium is formed, the storage stability is deteriorated and the heat transferable dye is likely to be precipitated. Dirt will occur. Also, if a2 / a1 exceeds 1.5, the amount of heat transferable dye near the surface of the dye layer 30 is too small compared to the inside, so that variation in color development sensitivity due to gradation increases and good transfer sensitivity is obtained during thermal transfer. I can't.

  The mixing ratio of the dye and the binder in the dye layer 30 is preferably (dye) / (binder) = 10/100 to 300/100 on a weight basis in any region in the depth direction. This is because when the ratio of (dye) / (binder) is less than 10/100, the amount of dye is too small and the color development sensitivity becomes insufficient and a good thermal transfer image cannot be obtained. This is because the solubility of the dye is extremely lowered, so that when the thermal transfer recording medium is formed, the storage stability is deteriorated and the dye is likely to be precipitated.

  Further, the dye layer 30 may contain additives such as an isocyanate compound, a silane coupling agent, a dispersant, a viscosity modifier, and a stabilizer as long as the performance is not impaired.

In the present invention, the release agent added to the dye layer 30 is composed of a polyether-modified silicone oil and a perfluoroalkyl compound. By adding the above two types of release agents, fusion between the dye layer and the transfer target can be efficiently prevented. Polyether-modified silicone oil and perfluoroalkyl compound alone can prevent the adhesion between the dye layer and the transferred material, but in recent high-speed printers using the sublimation transfer method, peeling lines and abnormal transfer may occur during thermal transfer. Generated, and satisfactory performance cannot be obtained.
In addition, even if the amount of release agent added is increased, there is also a release agent in the image bleed, background stain, foaming as an ink dye, and inside the dye layer and at the interface between the undercoat layer and the dye layer. As a result, printing wrinkles and abnormal transfer occur due to a decrease in heat resistance.
Here, by mixing the polyether-modified silicone oil and the perfluoroalkyl compound, the release agent component can be localized on the surface of the dye layer. You can prevent wearing.

When a polyether-modified silicone oil and a perfluoroalkyl compound are compared, the ability of preventing the fusion between the dye layer and the transfer target is better with the polyether-modified silicone oil, but the release agent is on the surface of the dye layer. In addition to being easily present not only inside the dye layer, there is a risk that the adhesion between the undercoat layer and the dye layer is lowered. On the other hand, the perfluoroalkyl compound is inferior in ability to prevent fusion between the dye layer and the transferred material, but is likely to be localized on the surface of the dye layer as compared with the polyether-modified silicone oil. This is because the surface tension of the perfluoroalkyl group contained in the fluorine-based mold release agent is low and has a high affinity with air.
Therefore, by mixing the polyether-modified silicone oil and the perfluoroalkyl compound, the release agent component can be localized on the surface of the dye layer with a small addition amount, thereby preventing the fusion between the dye layer and the transfer target. Is possible.

  Examples of the silicone oil include polyether-modified polysiloxane, polyether-modified polydimethylsiloxane, polyester-modified polysiloxane, polyester-modified polydimethylsiloxane, and aralkyl-modified polymethylalkylsiloxane. Polyether-modified silicone is preferable in terms of preventing the above.

The polyether-modified silicone is a silicone oil (polysiloxane), which is a polymer composed of siloxane bonds, in which a polyether which is a hydrophilic group is introduced into a side chain and / or a terminal. The siloxane chain may be linear, branched, or crosslinked. General silicone oil does not dissolve in water at all and exhibits water repellency. However, it is excellent in compatibility with both aqueous and non-aqueous systems due to its polyether modification. Exhibits excellent effects that cannot be obtained with.
Further, a different functional group-modified silicone oil in which an alkyl group, a reactive amino group, an epoxy group or the like is simultaneously introduced at the same time as the polyether chain can also be used according to the material configuration and purpose.

  The polyether-modified silicone of the present invention is commercially available under a general name, for example, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A manufactured by Shin-Etsu Silicone Co., Ltd. , KF-945, KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 , KF-6004, X-22-4952, X-22-4272, KF-6123. SH8700, SF8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203 manufactured by Toray Dow Corning. Although TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 (all are brand names) by Momentive Performance Materials, etc. can be used, it is not specifically limited.

As the perfluoroalkyl compound of the present invention, known compounds can be used, such as perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amino sulfonate, perfluoro Alkyl group / hydrophilic group-containing oligomer, perfluoroalkyl group / lipophilic group-containing oligomer, perfluoroalkyl group / (hydrophilic group and lipophilic group) -containing oligomer, perfluoroalkyl group / lipophilic group-containing urethane, perfluoro Alkyl phosphates, perfluoroalkyl carboxylates, perfluoroalkylamine compounds, perfluoroalkyl quaternary ammonium salts, perfluoroalkyl betaines, non-dissociable perfluoroalkyl compounds, etc.
The perfluoroalkyl compound of the present invention is commercially available under a general name. For example, MegaFuck F-470, MegaFuck F-471, MegaFuck F-472SF, and MegaFak manufactured by Dainippon Ink & Chemicals, Inc. F-474, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-478, Mega Fuck F-479, Mega Fuck F-480SF, Mega Fuck F-472, Mega Fuck F-484, Mega Fuck F- 484, Megafuck F-486, Megafuck F-487, Megafuck F-487, Megafuck F-172D, Megafuck F-178K, Megafuck F-178RM. Surflon S-242, S-243, S-420, S-386, S-611, S-651 manufactured by AGC Seimi Chemical Co., Ltd. Modifier F206, F606, F3636 of NOF Corporation. Novec TMFC-4430, FC-4432 (both product names) manufactured by Sumitomo 3M Limited can be used, but are not particularly limited.

  In addition, a release agent having a small molecular weight is likely to be localized on the surface of the dye layer. However, since the background stain and dye storage stability tend to be lowered, the molecular weight of the release agent is preferably 8000 or more.

The release agent has a release agent / binder resin weight ratio in the range from the outermost surface of the dye layer 30 to a depth of 0.1 t, b1, and a depth from the outermost surface of the dye layer of 0.1 to 1.0 t. When the weight ratio of the release agent / binder resin in the above range is b2, it is preferable that 0.5% by mass ≦ b1 ≦ 4.0% by mass and b2 ≦ 3.0% by mass.
When b1 is less than 0.5% by mass, since the absolute amount of the release agent on the surface of the dye layer 30 is small, fusion occurs between the dye layer 30 during printing and the receiving layer 120 of the thermal transfer image-receiving sheet 3, Sticking, peeling lines, and abnormal transfer are likely to occur. On the other hand, if b1 exceeds 4.0% by mass, problems such as scumming and bleeding, bubbling as ink dye, and precipitation of the dye are likely to occur. Further, the heat resistance of the dye layer is lowered, and printing wrinkles are likely to occur.
On the other hand, if b2 exceeds 3.0% by mass, the heat resistance of the dye layer is lowered, and printing wrinkles are likely to occur. Here, the upper limit of b2 is lower than b1 because the proportion of the dye layer in the film thickness is higher in b2. In addition, since there are no particular problems due to low b2, no lower limit is shown.
Note that b1 and b2 may be the same or different as long as they do not deviate from the above range.

The mixing ratio of the polyether-modified silicone oil and the perfluoroalkyl compound is preferably in the range of (polyether-modified silicone oil) / (perfluoroalkyl compound) = 9/1 to 6/4, especially 9 A range of 1 to 8/2 is preferred.
When the ratio is less than 9/1 (when the perfluoroalkyl compound is decreased), the release agent is less likely to be localized on the surface of the dye layer, and the dye layer and the transfer target are easily fused. When this ratio exceeds 6/4, the ratio of the polyether-modified silicone oil decreases, so that the dye layer and the transfer target are easily fused.

  The dye layer contains the above-mentioned dye, binder resin, polyether-modified silicone oil and perfluoroalkyl compound as essential components, and various other additives that are conventionally known may be added as necessary.

(Heat resistant slipping layer 40)
The heat resistant slipping layer 40 is prepared, for example, by preparing a coating solution for forming a heat resistant slipping layer by blending a binder, a functional additive that imparts releasability and slipperiness, a filler, a curing agent, a solvent, and the like. It is formed by coating and drying. The coating amount after drying of the heat resistant slipping layer 40 is suitably in the range of 0.1 g / m ² or more and 2.0 g / m ² or less.

  Examples of the binder contained in the heat resistant slipping layer 40 include polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, acrylic polyol, polyurethane acrylate, and polyester acrylate. , Polyether acrylate, epoxy acrylate, nitrocellulose resin, cellulose acetate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, and the like.

  Examples of the functional additive contained in the heat resistant slipping layer 40 include animal waxes, natural waxes such as plant waxes, synthetic hydrocarbon waxes, aliphatic alcohols and acid waxes, fatty acid esters and glycerite series. Synthetic wax such as wax, synthetic ketone wax, amine and amide wax, chlorinated hydrocarbon wax, alpha-olefin wax, higher fatty acid ester such as butyl stearate and ethyl oleate, sodium stearate, zinc stearate, Higher fatty acid metal salts such as calcium stearate, potassium stearate, magnesium stearate, long chain alkyl phosphate ester, polyoxyalkylene alkyl aryl ether phosphate ester or polyoxyalkylene alkyl ether phosphate ester Surfactants such as phosphoric acid esters, etc. can be mentioned.

Examples of the filler contained in the heat resistant slipping layer 40 include talc, silica, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, kaolin, clay, silicone particles, polyethylene resin particles, polypropylene resin particles, and polystyrene resin. Examples thereof include particles, polymethyl methacrylate resin particles, and polyurethane resin particles.
Examples of the curing agent contained in the heat resistant slipping layer 40 include isocyanates such as tolylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, and derivatives thereof, but are particularly limited. It is not a thing.

(Thermal transfer image receiving sheet 3)
As shown in FIG. 2, the thermal transfer image receiving sheet 3 has a configuration in which an intermediate layer 110 and a receiving layer 120 are laminated on a base sheet 100. The base material sheet 100 of the thermal transfer image receiving sheet 3 is preferably resin-coated paper in which both sides of the inner paper 130 serving as a core material are coated with polyethylene or polypropylene. That is, in this case, the base sheet 100 is provided with the resin coat layers 140 and 150 on both sides of the inner paper 130 as illustrated.
Below, each layer which comprises the thermal transfer image receiving sheet 3 of the thermal transfer recording material of this invention is described.

(Receptive layer 120)
The thermal transfer image-receiving sheet 3 of the present invention is obtained by forming a receiving layer 120 on a substrate sheet 100, and the receiving layer 120 is a vinyl chloride / vinyl acetate copolymer emulsion or a vinyl chloride / acrylic compound copolymer emulsion. It is formed using.
As long as the said receiving layer 120 was formed using the said emulsion, it may be formed directly on the base material sheet 100, a porous layer etc. which were formed on the base material sheet 100, etc. It may be formed on the intermediate layer 110.

The vinyl chloride / vinyl acetate copolymer emulsion used in the present invention comprises a vinyl chloride / vinyl acetate copolymer. The emulsion may contain only one type of the copolymer, or may contain two or more types having different monomer compositions, average molecular weights, and the like.
The vinyl chloride / vinyl acetate copolymer is not particularly limited as long as it is a copolymer of vinyl chloride and vinyl acetate, and can be copolymerized with these essential monomers in addition to vinyl chloride and vinyl acetate. Although the monomer may be polymerized in a small amount, it is preferably a vinyl chloride / vinyl acetate binary copolymer.

The vinyl chloride / acrylic compound copolymer emulsion used in the present invention comprises a vinyl chloride / acrylic compound copolymer. The emulsion may contain only one type of the copolymer, or may contain two or more types having different monomer compositions, average molecular weights, and the like.
The vinyl chloride / acrylic compound copolymer is not particularly limited as long as it is a copolymer composed of vinyl chloride and an acrylic compound, and can be copolymerized with these essential monomers in addition to vinyl chloride and the acrylic compound. Although a monomer may be copolymerized in a small amount, it is preferably a vinyl chloride / acrylic compound binary copolymer.
Hereinafter, “acrylic compound” means (meth) acrylic acid and / or an alkyl ester thereof.
Examples of the acrylic compound include acrylic acid, acrylates such as calcium acrylate, zinc acrylate, magnesium acrylate, and aluminum acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-ethoxyethyl. Acrylates such as acrylate, 2-hydroxyethyl acrylate, n-stearyl acrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, tridecyl methacrylate, Cyclohexyl methacrylate, triethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, trimethylol trimethacrylate Methacrylic acid esters of bread and the like.

Each of the above emulsions may contain, for example, an emulsifier such as a nonionic surfactant, a cationic surfactant, and an anionic surfactant, and the above emulsifier is 0% relative to 100 parts by weight of each copolymer. The amount is preferably 1 to 5 parts by weight. Further, in addition to the copolymer and the emulsifier described above, a known additive may be blended for the purpose of storage stability and the like.
In the present invention, as each of the above-mentioned emulsions, for example, commercially available products such as VINYBRAN 601 and VINYBRAN 276 (both manufactured by Nissin Chemical Industry Co., Ltd.) can be used.

The receiving layer 120 may contain a resin other than the above-described copolymer.
Examples of the other resins include polyolefin resins, polyvinyl resins, polyester resins, polycarbonate resins, polyamide resins, poly (meth) acrylic acid resins, cellulose derivative resins, and polyether resins.

Further, the receiving layer 120 may be formed by blending a release agent in order to prevent thermal fusion with the thermal transfer sheet during image formation.
Examples of the release agent include known ones such as silicone oil, phosphate ester compounds, and fluorine compounds, but silicone oil is particularly preferable.
Examples of the silicone oil include epoxy-modified silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, phenyl-modified silicone oil, epoxy / polyether-modified silicone oil, vinyl-modified silicone oil, hydrogen-modified silicone oil, etc. Modified silicone oil is preferred.
The release agent is preferably added so as to be about 0.5 to 30 parts by weight based on 100 parts by weight of each of the above-mentioned copolymers.

  The receiving layer 120 is formed by appropriately blending known additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a pigment, an antistatic agent, a plasticizer, and a hot-melt material. Also good.

  Examples of the antioxidant include chroman compounds, coumarone compounds, phenol compounds, hydroquinone derivatives, hindered amine derivatives, spiroindane compounds, sulfur compounds, phosphorus compounds, and the like known compounds for improving image durability. Can be mentioned.

  Examples of the ultraviolet absorber and the light stabilizer include 2- (2′-hydroxyphenyl) benzotriazole compounds.

  Examples of the filler include inorganic compound fine particles and organic compound fine particles. Examples of the inorganic compound fine particles include silica gel, calcium carbonate, titanium oxide, acidic clay, activated clay, and alumina. Examples of the organic compound fine particles include fluorine resin particles, guanamine resin particles, acrylic resin particles, and silicon resin. Examples thereof include resin particles such as particles.

  Examples of the pigment include known compounds such as titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

  Examples of the antistatic agent include known compounds such as a cationic surfactant, an anionic surfactant, a nonionic surfactant, a polymer antistatic agent, and conductive fine particles.

The plasticizer and the heat-meltable substance are usually added to promote transfer of the obtained thermal transfer image-receiving sheet.
Examples of the plasticizer include known compounds such as phthalic acid plasticizers, phosphate ester plasticizers, and polyester plasticizers.
Examples of the hot-melt material include known compounds having an action of promoting transfer, such as alcohols, ketones, and higher fatty acid esters.

(Base material sheet 100)
The substrate sheet 100 in the thermal transfer image receiving sheet 3 of the present invention is not particularly limited, and is a laminate obtained by laminating a paper or a film or sheet formed from a synthetic resin or the like, the paper, a film, a sheet, or the like. The body etc. can be mentioned.
In addition, a substrate sheet having a porous structure can also be suitably used in the present invention. The base sheet 100 has a role of holding the receiving layer 120 and heat is applied during thermal transfer. Therefore, the base sheet 100 preferably has a mechanical strength that does not hinder handling even in a heated state.

The paper is not particularly limited, and examples thereof include cellulose fiber paper, fine paper, art paper, coated paper, cast coated paper, glossy paper, impregnated paper, paperboard, and synthetic paper.
Examples of the synthetic paper include synthetic resin-impregnated paper, synthetic rubber latex-impregnated paper, condenser paper, and sulfuric acid paper.

  In the present invention, the base sheet 100 may include a sizing agent, a fixing agent, a paper strength enhancer, an antistatic agent, a dye, a pigment, a fluorescent whitening agent, an antioxidant, and an antifriction agent as necessary. Additives may be included.

Examples of the synthetic resin for forming the base sheet 100 include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, imide resins such as polycarbonate resins, polyurethane resins, polyimides, and polyetherimides, and cellulose derivatives. Olefin resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, styrene resins such as polystyrene, acrylic resins such as polyacryl and polyacrylate, polyamide resins such as various nylons, polyvinyl chloride and polyvinyl alcohol , Vinyl resins such as polyvinyl butyral, ketone resins such as polyetherketone and polyetheretherketone, sulfone resins such as polysulfone and polyethersulfone, tetrafluoroethylene-par Ruoro fluorine-based resins such as (alkyl vinyl ether) copolymer.
The base sheet 100 may be a film or sheet obtained by mixing one or more of the synthetic resins, or a film formed by adding a pigment, a filler, or the like to the synthetic resin. Or it may be a sheet.

  Examples of the laminate to be the base sheet 100 in the present invention include, for example, a laminate in which a film or sheet made of cellulose fiber paper and the synthetic resin is laminated, and one or more layers made of the synthetic resin. Examples include a laminated film or sheet.

  The laminate can be produced by a known lamination method such as dry lamination, wet lamination, or extrusion. For the purpose of improving the interlayer adhesion, each of the above layers can be appropriately subjected to primer treatment or corona discharge treatment on the surface thereof before being laminated.

The thickness of the base material sheet 100 in the thermal transfer image receiving sheet 3 of the present invention is usually 10 to 1000 μm, preferably 50 to 300 μm, and can be appropriately selected from the range.
In addition, in this specification, the thickness of the base material sheet 100 means the thickness of the whole laminated body, when the base material sheet 100 is a laminated body.

(Middle layer)
As described above, the thermal transfer image receiving sheet of the present invention may be one in which an intermediate layer is provided between the receiving layer 120 and the base sheet 100.
Hereinafter, the “intermediate layer” means all layers between the base sheet 100 and the receiving layer 120. By providing the intermediate layer, the thermal transfer image-receiving sheet 3 of the present invention is excellent in, for example, heat insulating properties, cushioning properties, barrier properties, interlayer adhesion properties, whiteness, hiding properties, antistatic properties, and the like. it can.

  Examples of the resin forming the intermediate layer and other polymers include polyurethane resin, polyester resin, polybutadiene resin, poly (meth) acrylate resin, epoxy resin, polyamide resin, rosin-modified phenol resin, terpene phenol resin, Examples include ethylene-vinyl acetate copolymer resins, polyolefin resins, cellulose resins, gelatin, and casein.

The intermediate layer may be a layer to which a water-soluble polymer is added, for example.
Examples of the water-soluble polymer include cellulose resins, starches, agar and other polysaccharides, proteins such as casein and gelatin, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer.・ Vinyl acetate- (meth) acrylic copolymer ・ Vinyl acetate-veova copolymer ・ (Meth) acrylic resin ・ Styrene- (meth) acrylic copolymer ・ Vinyl resin such as styrene resin, melamine resin ・ Urea resin ・Examples thereof include polyamide resins such as benzoguanamine resin, polyester, polyurethane and the like.
In the present invention, the water-soluble polymer is completely dissolved in an aqueous solvent (particle size 0.01 μm or less), colloidal dispersion (particle size 0.01 to 0.1 μm), emulsion (particle size 0.1 to 1 μm). Or the polymer which will be in the state of a slurry (particle size of 1 micrometer or more) is meant.

When a urethane resin, a polyester resin, or the like is added to the intermediate layer, a thermal transfer image receiving sheet excellent in interlayer adhesion can be obtained.
Moreover, when the thermoplastic resin having active hydrogen and a curing agent such as an isocyanate compound are used in combination as the intermediate layer, a thermal transfer image-receiving sheet having further excellent interlayer adhesion can be obtained.

For example, when a fluorescent brightener is added to the intermediate layer, white color can be imparted to the thermal transfer image receiving sheet.
The fluorescent brightening agent is not particularly limited, and conventionally known fluorescent brightening agents can be used. For example, stilbene fluorescent brighteners, distilbene fluorescent brighteners, benzoxazole fluorescent brighteners, styryl- Oxazole fluorescent whitening agent, pyrene-oxazole fluorescent whitening agent, coumarin fluorescent whitening agent, aminocoumarin fluorescent whitening agent, imidazole fluorescent whitening agent, benzimidazole fluorescent whitening agent, pyrazoline fluorescent whitening Examples include whitening agents, distyryl-biphenyl fluorescent whitening agents, and the like.
In the thermal transfer image-receiving sheet 3 of the present invention, the whiteness can be adjusted by appropriately selecting the type, addition amount and the like of the fluorescent brightening agent.

When titanium oxide is added to the intermediate layer, it is possible to obtain a thermal transfer image receiving sheet that conceals glare and unevenness of the base sheet.
Examples of the titanium oxide include rutile type titanium oxide and anatase type titanium oxide, and anatase type titanium oxide is preferable in terms of whiteness.
When the intermediate layer is made of the water-soluble resin described above, the titanium oxide may be added with a hydrophilic treatment applied to the surface, or a dispersant such as a surfactant may be appropriately added and dispersed.

  For example, when a conductive inorganic filler, an organic conductive agent or the like is added to the intermediate layer, a thermal transfer image-receiving sheet having antistatic properties can be obtained.

(Back layer 160)
The thermal transfer image-receiving sheet of the present invention has a back surface layer 160 on the surface opposite to the receiving layer 120 forming side of the base sheet 100 for the purpose of improving the mechanical transportability of the sheet, preventing curling, writing properties, preventing charging, and the like. You may have.
In the thermal transfer image receiving sheet 3 of the present invention, the back surface layer 160 may be composed of only one layer, or is composed of two or more layers having different compositions and the like. Also good.

The back layer 160 can be formed of a resin that forms the intermediate layer, a resin similar to that exemplified as the other polymer, or the like.
When the back layer 160 is formed, for example, in addition to the above exemplified resins, an appropriate amount of an organic filler or an inorganic filler is added, or when a resin having high lubricity such as a polyolefin resin or a cellulose resin is used, the transportability is increased. It is possible to obtain a thermal transfer image-receiving sheet with improved

  When the back layer 160 is formed, curling of the resulting thermal transfer image-receiving sheet can be prevented when a water-holding resin such as polyvinyl alcohol or polyethylene glycol is used as a main component.

  When the back layer 160 is formed, when fillers, pigments, and the like exemplified as the additive in the receiving layer 120 are blended, the writing property can be imparted to the obtained thermal transfer image receiving sheet.

The back layer 160 may be obtained by adding various antistatic agents such as conductive resins such as acrylic resins and fatty acid esters, sulfate esters, phosphate esters, ethylene oxide adducts, etc., in order to obtain an antistatic function. Good.
The amount of the antistatic agent used varies depending on the layer to which the antistatic agent is added, the antistatic agent used, and the like, but the surface electrical resistance value of the thermal transfer image-receiving sheet 3 is 1013Ω in order to prevent paper feeding troubles. / cm ² or less and so as, it is preferably used in an amount of usually 0.01 to 3 g / ^{m 2.}

If the said back surface layer 160 is the application amount of 3 g / m < ² > or less as a whole, the target various effects can be normally exhibited.

(Formation of Receptive Layer 120)
The receiving layer 120 in the thermal transfer image receiving sheet 3 of the present invention is formed using the above-mentioned emulsion. The method for forming the receiving layer 120 using the emulsion is not particularly limited. For example, a coating liquid is prepared from the emulsion described above, and the coating liquid is applied on a substrate sheet or an intermediate layer and dried. It can be produced by a known method such as a coating method.

The receiving layer 120 can be applied by a general method such as roll coating, bar coating, gravure coating, gravure reverse coating, comma coating, die coating, or lip coating.
In the coating of the receiving layer 120, the coating solution may be composed of only the above-mentioned emulsion, or the above-mentioned other resin, release agent and / or additive may be appropriately blended in the emulsion. May be prepared.

The coating liquid used in the coating of the receiving layer 120 has a solid concentration of usually 5% by mass or more. The upper limit of the solid content concentration is usually 50% by mass or less because if the concentration becomes too high, the storage stability may decrease and the viscosity may increase.
In the coating of the receiving layer, drying is preferably performed in the range of 50 to 150 ° C., although it varies depending on the composition of the coating solution used.
It is preferable to apply the coating solution so that the coating amount of the receiving layer is 0.5 to 10 g / m ² .

The method for forming the intermediate layer and the back layer 160 in the thermal transfer image-receiving sheet 3 of the present invention is not particularly limited, and examples thereof include a method for preparing and applying a coating liquid comprising the above-described constituent components.
In the above-described coating of the intermediate layer and the back layer 160, as a solvent for preparing a coating liquid, water, alcohols such as ethanol and propanol, cellosolves such as methyl cellosolve and ethyl cellosolve, toluene, xylene, and chloro Aromatics such as benzene, ketones such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran and dioxane, chlorine solvents such as chloroform and trichloroethylene, dimethylformamide and N-methyl Examples thereof include nitrogen-containing solvents such as pyrrolidone and dimethyl sulfoxide.

  In each coating for forming each layer in the present invention, a known resin surface modification such as primer treatment may be performed after coating in order to smooth the layer surface.

(Function and effect)
(1) In the thermal transfer recording medium 2 according to the present embodiment, the heat-resistant slipping layer 40 is provided on one surface of the substrate 10, and the undercoat layer 20 and the dye layer 30 are disposed in this order on the other surface of the substrate 10. The dye layer 20 includes at least a heat transferable dye, a binder resin, and a release agent, and the release agent is a polyether-modified silicone oil and a perfluoroalkyl compound, The ratio of the ether-modified silicone oil and the perfluoroalkyl compound is 9: 1 to 6: 4 by weight.
Thereby, generation | occurrence | production of a peeling line, abnormal transcription | transfer, a bleed, and soiling can be suppressed.
(2) In the thermal transfer recording medium 2 according to this embodiment, the polyether-modified silicone oil has a molecular weight of 8000 or more.
Thereby, generation | occurrence | production of a bleed and background dirt can be suppressed.
(3) Further, in the thermal transfer recording medium 2 according to the present embodiment, when the film thickness of the dye layer 30 is t, the heat transferable dye in the range from the outermost surface of the dye layer 30 to a depth of 0.1 t. 1.1 ≦ a2 / when the weight ratio to the binder resin is a1, and the weight ratio of the heat transferable dye to the binder resin in the range from the depth 0.1t to 1.0t from the outermost surface of the dye layer 30 is a2. It is assumed that a1 ≦ 1.5.
As a result, soiling can be prevented and good transfer sensitivity can be obtained during thermal transfer.
(4) In the thermal transfer recording medium 2 according to the present embodiment, the weight ratio of the release agent / binder resin in the range from the outermost surface of the dye layer 30 to the depth of 0.1 t is b1, and the outermost layer of the dye layer 30 is used. When the weight ratio of the release agent / binder resin in the depth range from 0.1 t to 1.0 t from the surface is b2, b1 is 0.5 mass% ≦ b1 ≦ 4.0 mass%, and b2 Is 0 mass% ≦ b2 ≦ 3.0 mass%.
Thereby, it is possible to suppress printing wrinkles, sticking, peeling lines, abnormal transfer, blurring, and background stains.
(5) In the thermal transfer image receiving sheet 3 according to the present embodiment, at least the base sheet 100, the porous layer 110, and the receiving layer 120 are laminated in this order, and the receiving layer 120 is made of vinyl chloride / vinyl acetate. A polymer or a vinyl chloride / acrylic compound copolymer is included.
Thereby, good transfer sensitivity can be obtained during thermal transfer.

  Below, the material used for each Example and each comparative example of this invention is shown. In the text, “part” or “%” is based on weight unless otherwise specified. The present invention is not limited to the examples.

Example 1
<Thermal transfer recording medium>
A 4.5 μm polyethylene terephthalate film is used as a substrate, and a coating solution for a heat-resistant slipping layer having the following composition is applied to one surface thereof by a gravure coating method with a coating amount of 1.0 g / m ² (film thickness: 0. 60 μm) and dried at 100 ° C. for 1 minute. Then, the base material with a heat resistant slipping layer was obtained by aging in a 40 degreeC environment for 1 week.
Next, the coating amount for the undercoat layer of the following composition is applied to the surface of the substrate with the heat resistant slipping layer on which the heat resistant slipping layer is not applied by a gravure coating method to 0.20 g / m ² . The undercoat layer was formed by coating at 100 ° C. for 2 minutes. Subsequently, the dye layer coating liquid B-1 was applied on the undercoat layer and dried at 90 ° C. for 1 minute to form the dye layer B. Further, the dye layer coating liquid A-1 was applied on the dye layer B and dried at 90 ° C. for 1 minute to form the dye layer A, thereby obtaining a thermal transfer recording medium. The film thickness ratio between the dye layer A and the dye layer B was 1: 9, and the total coating amount of the dye layer A and the dye layer B was 0.70 g / m ² .

<Coating liquid for heat resistant slipping layer>
Acrylic polyol resin 15.0 parts Zinc laurate 3.0 parts Talc (particle diameter (D50) 0.80 μm) 2.2 parts 2,6-tolylene diisocyanate prepolymer 4.8 parts Toluene 50. 0 parts, methyl ethyl ketone 20.0 parts, ethyl acetate 5.0 parts

<Coating liquid for undercoat layer>
・ Polyvinyl alcohol 2.50 parts ・ Polyvinylpyrrolidone 2.50 parts ・ Pure water 57.0 parts ・ Isopropyl alcohol 38.0 parts

<Dye layer coating liquid A-1>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.054 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.006 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.32 parts

<Dye layer coating liquid B-1>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.041 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.005 parts, toluene 45.0 parts, methyl ethyl ketone 44.955 parts

<Thermal transfer image receiving sheet>
Thermal transfer image-receiving sheet No. used for thermal transfer recording material 1 was produced.

<Thermal transfer image receiving sheet No. 1>
As a base sheet, synthetic paper (YUPO FPG-150, thickness 150 μm, manufactured by Oji Oil Chemical Co., Ltd.) was used. On one surface, a primer layer coating solution having the following composition was applied by a gravure coating method. It apply | coated so that it might become 0 g / m < ² >, and it was made to dry at 100 degreeC for 1 minute. Further, on the primer layer, the receiving layer coating liquid-1 having the following composition was applied by a gravure coating method so as to have a coating amount of 4.0 g / m ² and dried at 130 ° C. for 1 minute. Thermal transfer image receiving sheet No. 1 was obtained.

<Primer layer coating solution>
・ Polyester (Vaironal MD-1480, solid content concentration 25%, manufactured by Toyobo Co., Ltd.)
100 parts / water 25 parts

<Coating liquid for receiving layer-1>
・ Vinyl chloride / vinyl acetate copolymer emulsion (Viniblanc 601, solid concentration 43%, manufactured by Nissin Chemical Industry Co., Ltd.) 100 parts ・ Polyether modified silicone (KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.15 parts 124 parts of water

(Example 2)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-2 and the dye layer coating liquid B-2 having the following composition. Thus, a thermal transfer recording medium of Example 2 was obtained.

<Dye layer coating liquid A-2>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.32 parts

<Dye layer coating liquid B-2>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.009 parts, toluene 45.0 parts, methyl ethyl ketone 44.955 parts

(Example 3)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-3 and the dye layer coating liquid B-3 having the following composition. Thus, a thermal transfer recording medium of Example 3 was obtained.

<Dye layer coating liquid A-3>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.042 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.018 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.32 parts

<Dye layer coating liquid B-3>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.032 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.014 parts, toluene 45.0 parts, methyl ethyl ketone 44.955 parts

Example 4
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-4 and the dye layer coating liquid B-4 having the following composition. Thus, a thermal transfer recording medium of Example 4 was obtained.

<Dye layer coating liquid A-4>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.024 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.32 parts

<Dye layer coating liquid B-4>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.027 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.018 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.955 parts

(Example 5)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-5 and the dye layer coating liquid B-5 having the following composition. Thus, a thermal transfer recording medium of Example 5 was obtained.

<Dye layer coating solution A-5>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.096 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.024 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.26 parts

<Dye layer coating solution B-5>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.072 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.018 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.910 parts

(Example 6)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-6 and the dye layer coating liquid B-6 having the following composition. Thus, a thermal transfer recording medium of Example 6 was obtained.

<Dye layer coating liquid A-6>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.016 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.004 parts ・ Toluene 45.0 parts ・ Methyl ethyl ketone 46.36 parts

<Dye layer coating liquid B-6>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 10,000 manufactured by X-22-24272 Shin-Etsu Silicone) 0.012 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.003 parts, toluene 45.0 parts, methyl ethyl ketone 44.985 parts

(Example 7)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating solution A-7 and the dye layer coating solution B-7 having the following composition. Thus, a thermal transfer recording medium of Example 7 was obtained.

<Dye layer coating solution A-7>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000, manufactured by X-22-24957 Shin-Etsu Silicone) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.32 parts

<Dye layer coating solution B-7>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000 manufactured by X-22-4957 Shin-Etsu Silicone Co., Ltd.) 0.036 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.009 parts, toluene 45.0 parts, methyl ethyl ketone 44.955 parts

(Example 8)
A thermal transfer recording medium of Example 8 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating solution A-8 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating solution A-8>
・ C. I. Solvent Blue 63 5.44 parts, Polyvinyl acetal resin 4.00 parts, Polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 45.50 parts

Example 9
A thermal transfer recording medium of Example 9 was obtained in the same manner as in Example 2 except that, in the thermal transfer recording medium prepared in Example 2, the dye layer A was changed to the dye layer coating liquid A-9 having the following composition. .

<Dye layer coating solution A-9>
・ C. I. Solvent Blue 63 5.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 45.94 parts

(Example 10)
A thermal transfer recording medium of Example 10 was obtained in the same manner as in Example 2 except that, in the thermal transfer recording medium prepared in Example 2, the dye layer A was changed to the dye layer coating solution A-10 having the following composition. .

<Dye layer coating solution A-10>
・ C. I. Solvent Blue 63 4.28 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.66 parts

(Example 11)
A thermal transfer recording medium of Example 11 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating liquid A-11 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating liquid A-11>
・ C. I. Solvent Blue 63 4.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.94 parts

Example 12
The thermal transfer recording medium of Example 12 was obtained in the same manner as in Example 6 except that the dye layer B was changed to the dye layer coating solution B-8 having the following composition in the thermal transfer recording medium prepared in Example 6. .

<Dye layer coating solution B-8>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.016 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.004 parts, toluene 45.0 parts, methyl ethyl ketone 44.98 parts

(Example 13)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-12 and the dye layer coating liquid B-9 having the following composition. Thus, a thermal transfer recording medium of Example 13 was obtained.

<Dye layer coating solution A-12>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.092 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.023 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.265 parts

<Dye layer coating solution B-9>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.092 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.023 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.885 parts

(Example 14)
A thermal transfer recording medium of Example 14 was obtained in the same manner as in Example 5 except that, in the thermal transfer recording medium prepared in Example 5, the dye layer B was changed to the dye layer coating solution B-10 having the following composition. .

<Dye layer coating solution B-10>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.096 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.024 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.88 parts

(Example 15)
A thermal transfer recording medium of Example 15 was obtained in the same manner as in Example 6 except that the dye layer B was changed to the dye layer coating solution B-8 having the above composition in the thermal transfer recording medium prepared in Example 6. .

(Example 16)
A thermal transfer recording medium of Example 16 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating solution A-13 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating solution A-13>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.009 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.335 parts

(Example 17)
A thermal transfer recording medium of Example 17 was obtained in the same manner as in Example 5 except that, in the thermal transfer recording medium prepared in Example 5, the dye layer B was changed to the dye layer coating solution B-2 having the above composition. .

(Example 18)
In the heat-sensitive transfer recording medium prepared in Example 1, except that the dye layer A was changed to the dye layer coating liquid A-14 having the following composition and the dye layer B was changed to the dye layer coating liquid B-10 having the above composition. In the same manner as in Example 1, the thermal transfer recording medium of Example 18 was obtained.

<Dye layer coating solution A-14>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.100 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.025 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.255 parts

(Example 19)
A thermal transfer recording medium of Example 19 was obtained in the same manner as in Example 18 except that the dye layer A was changed to the dye layer coating solution A-15 having the following composition in the thermal transfer recording medium prepared in Example 18. .

<Dye layer coating solution A-15>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.120 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.040 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.220 parts

(Example 20)
As a thermal transfer image receiving sheet, thermal transfer image receiving sheet No. 1 having the following composition was used. A thermal transfer recording material of Example 20 was obtained in the same manner as Example 2 except that No. 2 was used.

<Thermal transfer image receiving sheet No. 2>
The thermal transfer image receiving sheet No. 1 was used except that the receiving layer coating solution-2 having the following composition was used instead of the receiving layer coating solution-1. As in the case of thermal transfer image receiving sheet No. 2 was produced.

<Coating liquid for receiving layer-2>
・ Vinyl chloride / acrylic compound copolymer emulsion (Viniblanc 276,
Solid content 45%, manufactured by Nissin Chemical Industry Co., Ltd.) 100 parts, polyether-modified silicone (KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.15 parts, water 124 parts

(Comparative Example 1)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-16 and the dye layer coating liquid B-11 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 1 was obtained.

<Dye layer coating solution A-16>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 10,000 manufactured by X-22-4272 Shin-Etsu Silicone Co., Ltd.) 0.120 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.26 parts

<Dye layer coating solution B-11>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 10,000 manufactured by X-22-24272 Shin-Etsu Silicone) 0.090 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.910 parts

(Comparative Example 2)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-17 and the dye layer coating liquid B-12 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 2 was obtained.

<Dye layer coating solution A-17>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000, manufactured by X-22-24957 Shin-Etsu Silicone Co., Ltd.) 0.120 parts, toluene 45.0 parts, methyl ethyl ketone 46.26 parts

<Dye layer coating solution B-12>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000 manufactured by X-22-24957 Shin-Etsu Silicone Co., Ltd.) 0.090 parts, toluene 45.0 parts, methyl ethyl ketone 44.910 parts

(Comparative Example 3)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-18 and the dye layer coating liquid B-13 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 3 was obtained.

<Dye layer coating solution A-18>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000, manufactured by X-22-24957 Shin-Etsu Silicone Co., Ltd.) 0.280 parts, 44.86 parts of toluene, 46.24 parts of methyl ethyl ketone

<Dye layer coating solution B-13>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 5000, manufactured by X-22-24957 Shin-Etsu Silicone Co., Ltd.) 0.210 parts, toluene 44.86 parts, methyl ethyl ketone 44.930 parts

(Comparative Example 4)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-19 and the dye layer coating liquid B-14 having the following composition, respectively. Thus, a thermal transfer recording medium of Comparative Example 4 was obtained.

<Dye layer coating solution A-19>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.060 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.060 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.26 parts

<Dye layer coating solution B-14>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.045 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.045 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.91 parts

(Comparative Example 5)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-20 and the dye layer coating liquid B-15 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 5 was obtained.

<Dye layer coating solution A-20>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.140 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.140 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.10 parts

<Dye layer coating solution B-15>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.105 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.105 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.79 parts

(Comparative Example 6)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-21 and the dye layer coating liquid B-16 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 6 was obtained.

<Dye layer coating liquid A-21>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.084 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.26 parts

<Dye layer coating solution B-16>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.027 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.063 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.91 parts

(Comparative Example 7)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-22 and the dye layer coating liquid B-17 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 7 was obtained.

<Dye layer coating liquid A-22>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.084 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.196 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.10 parts

<Dye layer coating solution B-17>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.063 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.147 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.79 parts

(Comparative Example 8)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that Dye Layer A and Dye Layer B were changed to Dye Layer Coating Liquid A-23 and Dye Layer Coating Liquid B-18 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 8 was obtained.

<Dye layer coating solution A-23>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.120 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.260 parts

<Dye layer coating solution B-18>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.090 parts · Toluene 45.00 parts · Methyl ethyl ketone 44.910 parts

(Comparative Example 9)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-24 and the dye layer coating liquid B-19 having the following composition, respectively. Thus, a thermal transfer recording medium of Comparative Example 9 was obtained.

<Dye layer coating liquid A-24>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.280 parts · Toluene 44.86 parts · Methyl ethyl ketone 46.240 parts

<Dye layer coating solution B-19>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.210 parts · Toluene 44.86 parts · Methyl ethyl ketone 44.930 parts

(Comparative Example 10)
A thermal transfer recording medium of Comparative Example 10 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating liquid A-25 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating liquid A-25>
・ C. I. Solvent Blue 63 6.70 parts · Polyvinyl acetal resin 4.00 parts · Polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.24 parts

(Comparative Example 11)
The thermal transfer recording medium of Comparative Example 11 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating solution A-26 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating liquid A-26>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.94 parts

(Comparative Example 12)
A thermal transfer recording medium of Comparative Example 12 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating liquid A-27 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating liquid A-27>
・ C. I. Solvent Blue 63 5.70 parts, Polyvinyl acetal resin 4.00 parts, Polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 45.24 parts

(Comparative Example 13)
The thermal transfer recording medium of Comparative Example 13 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating solution A-28 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating liquid A-28>
・ C. I. Solvent Blue 63 3.87 parts Polyvinyl acetal resin 4.00 parts Polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 47.07 parts

(Comparative Example 14)
A thermal transfer recording medium of Comparative Example 14 was obtained in the same manner as in Example 2 except that the dye layer A was changed to the dye layer coating liquid A-29 having the following composition in the thermal transfer recording medium prepared in Example 2. .

<Dye layer coating solution A-29>
・ C. I. Solvent Blue 63 3.75 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272 Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.012 parts · Toluene 45.0 parts · Methyl ethyl ketone 47.19 parts

(Comparative Example 15)
A thermal transfer recording medium of Comparative Example 15 was obtained in the same manner as in Example 6 except that the dye layer A was changed to the dye layer coating liquid A-30 having the following composition in the thermal transfer recording medium prepared in Example 6. .

<Dye layer coating solution A-30>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(Molecular weight 10,000 manufactured by X-22-24272 Shin-Etsu Silicone) 0.012 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.003 parts, toluene 45.0 parts, methyl ethyl ketone 46.365 parts

(Comparative Example 16)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-31 and the dye layer coating liquid B-20 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 16 was obtained.

<Dye layer coating liquid A-31>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.104 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.026 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.25 parts

<Dye layer coating solution B-20>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.104 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.026 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.87 parts

(Comparative Example 17)
In the thermal transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-32 and the dye layer coating liquid B-21 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 17 was obtained.

<Dye layer coating liquid A-32>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.112 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.028 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.24 parts

<Dye layer coating liquid B-21>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.112 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.028 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.86 parts

(Comparative Example 18)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-33 and the dye layer coating liquid B-22 having the following composition. Thus, a thermal transfer recording medium of Comparative Example 18 was obtained.

<Dye layer coating liquid A-33>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, toluene 45.0 parts, methyl ethyl ketone 46.38 parts

<Dye layer coating liquid B-22>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, toluene 45.0 parts, methyl ethyl ketone 45.0 parts

(Comparative Example 19)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as in Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating solution A-30 and the dye layer coating solution B-22 having the above-described composition. Thus, a thermal transfer recording medium of Comparative Example 19 was obtained.

(Comparative Example 20)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-30 and the dye layer coating liquid B-8 having the above composition. Thus, a thermal transfer recording medium of Comparative Example 20 was obtained.

(Comparative Example 21)
A thermal transfer recording medium of Comparative Example 21 was obtained in the same manner as in Example 5 except that the thermal transfer recording medium prepared in Example 5 was replaced with the dye layer coating solution B-23 having the following composition. .

<Dye layer coating solution B-23>
・ C. I. Solvent Blue 63 6.00 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.100 part perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.025 parts · Toluene 45.0 parts · Methyl ethyl ketone 44.875 parts

(Comparative Example 22)
In the heat-sensitive transfer recording medium prepared in Example 1, the same as Example 1 except that the dye layer A and the dye layer B were changed to the dye layer coating liquid A-14 and the dye layer coating liquid B-23 having the above-described composition. Thus, a thermal transfer recording medium of Comparative Example 22 was obtained.

(Comparative Example 23)
The thermal transfer recording medium of Comparative Example 23 was obtained in the same manner as in Example 14 except that the dye layer A was changed to the dye layer coating liquid A-34 having the following composition in the thermal transfer recording medium prepared in Example 14. .

<Dye layer coating liquid A-34>
・ C. I. Solvent Blue 63 4.62 parts, polyvinyl acetal resin 4.00 parts, polyether-modified silicone oil
(X-22-24272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.128 parts perfluoroalkyl compound
(Megafac F-569 DIC Corporation) 0.042 parts · Toluene 45.0 parts · Methyl ethyl ketone 46.210 parts

(Comparative Example 24)
As a thermal transfer image receiving sheet, thermal transfer image receiving sheet No. 1 having the following composition was used. A thermal transfer recording material of Comparative Example 24 was obtained in the same manner as in Example 2 except that No. 3 was used.

<Thermal transfer image receiving sheet No. 3>
The thermal transfer image receiving sheet No. 1 was used except that the receiving layer coating solution-3 was used instead of the receiving layer coating solution-1. As in the case of thermal transfer image receiving sheet No. 3 was produced.
<Receiving layer coating solution-3>
・ Polyester (Vylonal MD-1200, solid content concentration 30%, manufactured by Toyobo Co., Ltd.)
100 parts, polyether-modified silicone (KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 parts, water 56 parts

(Comparative Example 25)
As a thermal transfer image receiving sheet, thermal transfer image receiving sheet No. 1 having the following composition was used. A thermal transfer recording material of Comparative Example 25 was obtained in the same manner as in Example 2 except that No. 4 was used.

<Thermal transfer image receiving sheet No. 4>
The thermal transfer image receiving sheet No. 1 was used except that the receiving layer coating solution-4 was used instead of the receiving layer coating solution-1. As in the case of thermal transfer image receiving sheet No. 4 was produced.

<Receiving layer coating solution-4>
・ Polyester (Vylonal MD-1500, solid content concentration 30%, manufactured by Toyobo Co., Ltd.)
100 parts, polyether-modified silicone (KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 parts, water 56 parts

(Comparative Example 26)
As a thermal transfer image receiving sheet, thermal transfer image receiving sheet No. 1 having the following composition was used. A heat-sensitive transfer recording material of Comparative Example 26 was obtained in the same manner as in Example 2 except that 5 was used.

<Thermal transfer image receiving sheet No. 5>
The thermal transfer image receiving sheet No. 1 was used except that the receiving layer coating solution-5 was used instead of the receiving layer coating solution-1. As in the case of thermal transfer image receiving sheet No. 5 was produced.

<Receptive layer coating solution-5>
・ Acrylic resin (AQ4635, solid content concentration 30%, manufactured by Daicel Chemical Industries) 100 parts ・ Polyether-modified silicone (KF-615A, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 parts ・ Water 56 parts

  The composition of the coating liquid for the dye layer used for coating the dye layer A and the dye layer B of the thermal transfer recording medium in Examples 1 to 20 and Comparative Examples 1 to 26 and the thermal transfer image receiving sheet No. Are shown in Tables 1 and 2.

<Evaluation of transfer sensitivity>
Tables 3 and 4 show the results of printing the thermal transfer recording materials of Examples 1 to 20 and Comparative Examples 1 to 26 using a thermal simulator and evaluating the transfer sensitivity.
Here, pattern images having different gradations from white to solid were printed under the following conditions, and measured with a chromaticity meter (Macbeth densitometer RD-918; manufactured by Macbeth) to evaluate the transfer sensitivity.
・ Printing environment: 23 ℃ 50% RH
・ Applied voltage: 24V
・ Printing speed: 10 inch / sec
Print density: 300 dpi main scanning, 300 dpi sub scanning
The evaluation criteria are as follows, and Δ or higher is a level where there is no practical problem.
○: Excellent transfer sensitivity △: Transfer sensitivity is slightly poor ×: Transfer sensitivity is poor

<Print wrinkle evaluation>
Using the sensitive transfer recording materials of Examples 1 to 20 and Comparative Examples 1 to 26, solid printing was performed under the same conditions as in the above transfer sensitivity evaluation using a thermal simulator, and the results of evaluating printing wrinkles are shown in Tables 3 and 4 Show.
The evaluation criteria are as follows, and Δ is a practically satisfactory level.
◯: No print defect due to wrinkles on the printed material Δ: Print image has slight print defects due to wrinkles ×: Print image has print defects due to wrinkles

<Evaluation of sticking / peeling line / abnormal transfer>
With respect to the thermal transfer recording media of Examples 1 to 20 and Comparative Examples 1 to 26, a thermal transfer recording medium cured at room temperature and a transfer target were used, and a black gradation was obtained with a thermal simulator in an environment of 48 ° C. and 5%. Thirty sheets were printed, and the presence or absence of sticking or peeling lines between the thermal transfer recording medium and the thermal transfer image receiving sheet and abnormal transfer were evaluated. The printing conditions are the same as in the above transfer sensitivity evaluation except that the printing environment is 48 ° C. and 5%. The evaluation results are shown in Tables 3 and 4.
The evaluation criteria are as follows, and Δ or higher is a level where there is no practical problem. In addition, since the thing with sticking x was not able to be evaluated by sticking of a thermal transfer recording medium and a thermal transfer image receiving sheet, it was made impossible to evaluate all others. Similarly, when the abnormal transfer was x, the evaluation was not possible because the dye layer was transferred to the subject and could not be evaluated.
○: No peeling line / abnormal transfer to the transfer object is observed Δ: Very little peeling line / abnormal transfer to the transfer object is observed ×: No peeling line / abnormal transfer to the transfer object Approved on all sides

<Evaluation of smudge and background print>
Using the heat-sensitive transfer recording materials of Examples 1 to 20 and Comparative Examples 1 to 26, printing was performed with a thermal simulator, and bleeding of printed matter and background contamination were evaluated. The printing conditions were the same as those in the transfer sensitivity evaluation, and the evaluation image used was a natural image (person image) for blurring and a white solid image for background stain. The evaluation results are shown in Tables 3 and 4.
The evaluation criteria are as follows, and Δ or higher is a level where there is no practical problem.
○: Smudge / stain is not observed △: Smudge / stain is slightly observed ×: Smudge / stain is observed on the entire surface

Examples 1 to 20 in which a polyether-modified silicone oil and a perfluoroalkyl compound are mixed in a mass ratio of 9: 1 to 6: 4 are Comparative Examples 1 to 3, 8, 9 and a mass ratio in which each is used alone. As compared with Comparative Examples 4 to 7 that were outside the range of 9: 1 to 6: 4, it was found that no peeling line, sticking, abnormal transfer, blurring, or soiling occurred.
In Comparative Example 18 in which the polyether-modified silicone oil and the perfluoroalkyl compound were not added, sticking occurred.
From the above, it has been found that it is effective to add both a polyether-modified silicone oil and a perfluoroalkyl compound for the prevention of peeling lines, sticking, abnormal transfer, blurring, and soiling.
Furthermore, from the comparison between Example 2 where the molecular weight of the polyether-modified silicone oil is 8000 or more and Example 7 where the molecular weight is 8000 or less, the one where the molecular weight of the polyether-modified silicone oil is larger is more effective against bleeding and soiling. I understood that.

Examples 2 and 8 to 11 in which a2 / a1 is different when the weight ratio of the dye (CI solvent blue) / binder resin (polyvinyl acetal resin) of the dye layer A and the dye layer B is a1 and a2, respectively. Comparative Examples 10 to 14 were compared.
As a result, background staining occurred in Comparative Examples 10 to 12 where a2 / a1 was less than 1.1, and transfer sensitivity deteriorated in Comparative Examples 13 and 14 where a2 / a1 exceeded 1.5. On the other hand, in Examples 2 and 8 to 11 in which a2 / a1 was 1.1 or more and 1.5 or less, it was confirmed that no background staining occurred and transfer sensitivity was good.
From this, it has been found that if a2 / a1 is 1.1 or more and 1.5 or less, background fouling does not occur and a thermal transfer recording material having a good transfer sensitivity can be provided.

Examples 12 to 12 were prepared by comparing the composition of the release agent and the weight ratio of the release agent / binder resin of the dye layer A and the dye layer B (b1 = b2) by changing the weight ratio. 16 and Comparative Examples 15-17.
As a result, sticking occurred in Comparative Example 15 in which the weight ratio was less than 0.5% by mass, and printing wrinkles, blurring, and soiling occurred in Comparative Example 16 and Comparative Example 17 in which the weight ratio exceeded 3.0% by weight. Occurred. On the other hand, in Examples 12 to 16 in which the weight ratio was 0.5% by mass or more and 3.0% by mass or less, it was confirmed that sticking, printing wrinkles, blurring, and soiling did not occur.
Therefore, if the weight ratio of the release agent / binder resin in the dye layer is 0.5% by mass or more and 3.0% by mass or less, the thermal transfer recording material does not cause sticking, printing wrinkles, blurring, and soiling. It was found that can be provided.

Examples 2 and 17 to 19 and Comparative Examples 19 to 19 were compared by changing the weight ratio of those having the same release agent composition but having different release agent / binder resin weight ratios of the dye layer A and the dye layer B. 21 and 23.
In Comparative Examples 19 and 20 in which the weight ratio of the dye layer A is less than 0.5% by mass, sticking occurs, and in Comparative Example 23 in which the weight ratio of the dye layer A exceeds 4.0% by mass, printing wrinkles and blurring are caused. Dirt occurred.
In Comparative Example 21 in which the weight ratio of the dye layer B exceeds 3.0% by mass, printing wrinkles were confirmed.
On the other hand, in Examples 2 and 17 to 19 in which the weight ratio of the dye layer A is 0.5% by mass or more and 4.0% by mass or less and the weight ratio of the dye layer B is 3.0% by mass or less. There was no sticking, printing wrinkles, blurring, or soiling, and even if only a slight amount was confirmed, there was no problem in practical use.
From this, the weight ratio of the release agent / binder resin of the dye layer A is 0.5% by mass or more and 4.0% by mass or less, and the weight ratio of the release agent / binder resin of the dye layer B is 3. It has been found that when the content is 0% by mass or less, it is possible to provide a heat-sensitive transfer recording material that does not cause sticking, printing wrinkles, blurring, and soiling.

Examples 2 and 20 and Comparative Examples 24 to 26 having the same thermal transfer recording medium and different thermal transfer image receiving sheet receiving layers were compared.
As a result, in Examples 2 and 22 in which a vinyl chloride / vinyl acetate copolymer emulsion or a vinyl chloride / acrylic compound copolymer emulsion was used for the receiving layer of the thermal transfer image-receiving sheet, the transfer sensitivity was good. It was confirmed that the transfer sensitivity deteriorated in Comparative Examples 24-26 using No ..
From this, it was found that if a vinyl chloride / vinyl acetate copolymer emulsion or a vinyl chloride / acrylic compound copolymer emulsion is used for the receiving layer of the thermal transfer image receiving sheet, good transfer sensitivity can be obtained.

  Although the present invention has been described with reference to a limited number of embodiments, the scope of rights is not limited thereto, and modifications of each embodiment based on the above disclosure are obvious to those skilled in the art.

  The thermal transfer recording medium obtained by the present invention can be used in a sublimation transfer type printer, and various images can be easily formed in full color in combination with high speed and high functionality of the printer. For this reason, it can be widely used for self-printing of digital cameras, cards such as identification cards, output materials for amusement, and the like.

1: Thermal transfer recording material 2: Thermal transfer recording medium 3: Thermal transfer image receiving sheet 10: Base material 20: Undercoat layer 30: Dye layer 40: Heat-resistant slip layer 100: Base material sheet 110: Porous layer 120: Receptive layer 130 : Inner paper 140: Resin coat layer 150: Resin coat layer 160: Back layer

Claims (5)

  At least a base sheet, a porous layer, and a receiving layer are laminated in this order, and a thermal transfer image receiving sheet, and at least one dye layer on one side of the base, and on the other side of the base A thermal transfer recording material comprising a combination of at least a heat-sensitive transfer recording medium having a heat resistant slipping layer, wherein the receiving layer contains a vinyl chloride / vinyl acetate copolymer or a vinyl chloride / acrylic compound copolymer, and the dye layer Includes a heat transfer dye, a binder resin, and a release agent, and the release agent comprises a polyether-modified silicone oil and a perfluoroalkyl compound, and a ratio of the polyether-modified silicone oil and the perfluoroalkyl compound is The mass ratio is 9: 1 to 6: 4, and when the thickness of the dye layer is t, the range from the outermost surface of the dye layer to a depth of 0.1 t and 1.0 from there Thermal transfer recording material, wherein the weight ratio is different for the binder resin of said heat migrating dye in a range up. The weight ratio of the heat transferable dye to the binder resin in the range from the outermost surface of the dye layer to a depth of 0.1 t is a1, and the depth from the outermost surface of the dye layer is from 0.1 t to 1.0 t. 2. The thermal transfer recording material according to claim 1, wherein the relationship of the following formula (1) is established when a weight ratio of the heat transferable dye to the binder resin in a range is a2.
1.1 ≦ a2 / a1 ≦ 1.5 (1)   3. The thermal transfer recording material according to claim 1, wherein a content ratio of the release agent is 0.5 to 3.0 mass% with respect to the binder resin. The weight ratio of the release agent to the binder resin in the range from the outermost surface of the dye layer to the depth of 0.1 t is b1, and the depth from the outermost surface of the dye layer is in the range of 0.1 to 1.0 t. The thermal transfer according to claim 1 or 2, wherein the relationship of the following formulas (1), (2), and (3) holds when the weight ratio of the release agent to the binder resin in b2 is b2. Recording material.
b1 ≠ b2 (1)
0.5% by mass ≦ b1 ≦ 4.0% by mass (2)
0% by mass ≦ b2 ≦ 3.0% by mass (3)   The thermal transfer recording material according to any one of claims 1 to 4, wherein the polyether-modified silicone oil has a molecular weight of 8000 or more.