JP4889671B2 - Method for producing thermal transfer image-receiving sheet - Google Patents

Description

  The present invention relates to a method for producing a thermal transfer image-receiving sheet, and more particularly to a method for producing a thermal transfer image-receiving sheet having high sensitivity and few image failures.

  Conventionally, various thermal transfer recording methods are known, and among them, the dye diffusion transfer recording method is attracting attention as a process capable of producing a color hard copy closest to the image quality of a silver salt photograph (for example, Non-Patent Document 1 and 2). In addition, it has the advantages of being dry, being able to visualize directly from digital data, and being easy to duplicate, compared to silver salt photography.

  In this dye diffusion transfer recording system, a heat-sensitive transfer sheet (hereinafter also referred to as an ink sheet) containing a dye is superposed on a heat-sensitive transfer image-receiving sheet (hereinafter also referred to as an image-receiving sheet), and then heat generation is controlled by an electrical signal. The ink sheet is heated by a thermal head to transfer the dye in the ink sheet to the image receiving sheet, and image information is recorded. By recording three colors of cyan, magenta, and yellow, the color is recorded. A color image having a continuous change in shading can be transferred and recorded.

In such a dye diffusion transfer type recording system, it has long been known that it is important to give the image receiving sheet high heat insulation and cushioning in order to obtain a good image (for example, non-patent literature). 1 and 2).
Therefore, in order to provide heat insulation and cushioning properties, a composite support using a biaxially stretched polyolefin film containing microvoids may be used as the base material of the thermal transfer image-receiving sheet. However, in this method, the residual stress at the time of stretching is relaxed and contracted by heat at the time of printing and heat at the time of coating the receiving layer, and wrinkles and curls are generated on the heat-sensitive transfer image-receiving sheet.

  Other methods for imparting heat insulation and cushioning to the heat-sensitive transfer image-receiving sheet have been studied. For example, a method for forming a foamed layer (for example, Patent Document 1) composed of a resin and a foaming agent between a support and a receiving layer, and a microcapsule-shaped hollow polymer and an organic solvent-resistant polymer as main components (Patent Document 2). Since these methods can form a heat insulating layer on a substrate by a coating method, there is an advantage that generation of wrinkles and curls can be suppressed in the heat-sensitive transfer image-receiving sheet seen on the composite support. However, it is difficult to obtain a uniform and smooth heat-sensitive transfer image-receiving sheet, and there are drawbacks such as defective transfer, white spots, rough surface, and poor protective layer adhesion. As a means for solving this problem, when forming an intermediate layer containing a resin containing hollow particles as a main component on a sheet-like base material, after applying the intermediate layer-forming paint on the sheet-like base material, the coated surface is used as a cast drum. A method for forming an image receiving sheet by pressure bonding (Patent Document 3) has also been proposed. However, although this method can obtain sufficient smoothness, the manufacturing process becomes complicated and disadvantageous in terms of productivity.

  For such a problem, for example, in a heat-sensitive transfer image-receiving sheet having a heat insulating layer and a receiving layer on a substrate, the heat insulating layer contains a hollow polymer, and the hollow polymer content is 65% by mass or more, A thermal transfer image-receiving sheet is disclosed in which a heat-insulating layer and a layer on the side of the receiving layer adjacent thereto are formed by simultaneous multilayer coating (Patent Document 4). In the proposed method, a high filling rate of particles must be ensured in order to obtain a sufficient heat insulating effect, and the coating liquid has a high hollow polymer ratio. However, the simultaneous multi-layer coating causes mixing of the heat-insulating layer and the coating liquid adjacent to the heat-insulating layer and the movement of water, resulting in unevenness due to local changes in viscosity, resulting in the outermost surface. In some cases, an image failure occurs due to the smoothness of the image. Such a phenomenon has not conventionally occurred in a silver halide photographic light-sensitive material that has been simultaneously coated with multiple layers. This is technically different in that a coating solution containing a bulky solid substance at a high concentration is applied simultaneously, and it has been difficult to solve the problem. Furthermore, in simultaneous multi-layer coating using a water-based coating solution, the coating passes through a drying step after coating, but a coating solution that does not contain bulky solids is simultaneously layered on the upper layer side of the coating solution that contains bulky solids at a high concentration. In the case of coating, the volume shrinkage rate at the time of drying is different, so that there is a problem that the surface of the coating film is cracked after drying, leading to image failure.

  On the other hand, in the heat-sensitive transfer image-receiving sheet having a heat insulating layer and a receiving layer on a substrate, the heat insulating layer contains a hollow polymer, and the content of the hollow polymer contained in the heat insulating layer is 40% by mass or more. A thermal transfer image-receiving sheet using a vinyl chloride / vinyl acetate copolymer emulsion or a vinyl chloride / acrylic compound copolymer emulsion as a layer is disclosed (Patent Document 5). In the proposed method, the heat insulating layer and the receiving layer are formed by sequential coating. However, since the heat insulating layer is used at a high filling rate so as to also use the voids between the hollow polymer particles in order to obtain a sufficient heat insulating effect, when the layer on the receiving layer side is sequentially applied on the heat insulating layer, the heat insulating layer is formed. There has been a problem that the coating solution of the layer on the receiving layer side penetrates into the voids between the hollow polymer particles on the outermost surface of the heat insulating layer that functions most effectively, thereby reducing the heat insulating effect.

Against this background, high-density printing characteristics are achieved by utilizing the voids of the hollow polymer by simultaneous multilayer coating, and high smoothness is achieved by eliminating irregularities due to interfacial mixing at the liquid interface of multilayer coating. Such a thermal transfer image-receiving sheet and a method for producing the same have been strongly desired. As a solution method to eliminate unevenness at the time of coating, a method for producing a thermal transfer sheet (Patent Document 6) that makes the coating film uniform by controlling the viscosity of the coating solution, or by reducing the film surface temperature at the time of coating, a single layer coating An inkjet recording paper manufacturing method that suppresses film disturbance (Patent Document 7) is disclosed, but both are inventions related to single-layer coating, which eliminates unevenness caused by interfacial mixing of two adjacent layers in multilayer coating. Is not mentioned. In Patent Documents 4 and 6, no consideration is given to preventing cracking due to the difference in volume shrinkage, and the optimum temperature range during drying is not described.
Japanese Patent No. 2554196 Japanese Patent No. 3226167 JP-A-5-8572 JP 2006-88691 A JP 2006-264092 A JP 2006-130810 A JP 2001-10207 A “New development of information recording (hard copy) and its materials”, published by Toray Research Center, Inc., 1993, p. 241-285 “Development of printer materials”, issued by CMC Co., Ltd., 1995, p. 180

  The present invention eliminates the above-mentioned problems derived from the heat-insulating layer of the thermal transfer image-receiving sheet prepared by the conventional simultaneous multi-layer coating method, has high density printing characteristics, and unevenness due to interfacial mixing and a difference in volume shrinkage. It is an object of the present invention to provide a thermal transfer recording image receiving sheet and a method for producing the same, in which there are few image failures due to cracks caused by the crack.

As a result of intensive studies, the present inventors have found that the above problem can be achieved by the following means.
(1) A thermal transfer image-receiving sheet having at least a heat insulating layer and a receiving layer on a support, the receiving layer containing at least one polymer latex, the heat insulating layer containing at least one hollow polymer, This is a method for producing a thermal transfer image-receiving sheet in which two layers are formed by simultaneous multilayer coating. The production method includes a coating step and a drying step, and at least 60% of the total water content is dried during the drying step. A method for producing a heat-sensitive transfer image-receiving sheet, wherein the film surface temperature is kept at 5 ° C. or higher and 20 ° C. or lower during the time.
(2) The method for producing a thermal transfer image-receiving sheet as described in (1), wherein 60% of the total water content is dried within 1 minute during the drying step.
(3) The method for producing a heat-sensitive transfer image-receiving sheet as described in (1) or (2), wherein the receptor layer and / or the heat insulating layer contains a water-soluble polymer.
(4) The method for producing a thermal transfer image-receiving sheet as described in (3), wherein the water-soluble polymer is polyvinyl alcohol or gelatin.

  The heat-sensitive transfer image-receiving sheet of the present invention has high sensitivity and few image failures. Further, it can be manufactured at low cost.

Hereinafter, the present invention will be described in detail.
The heat-sensitive transfer image-receiving sheet of the present invention has at least one heat insulating layer containing at least one hollow polymer on the support, at least one receiving layer containing at least one polymer latex, and at least adjacent heat insulating layers. And the receiving layer side layer are formed by simultaneous multilayer coating. The layer on the side of the receiving layer adjacent to the heat insulating layer may be a receiving layer or an intermediate layer having other functions. Moreover, the heat insulation layer and the receiving layer may each be formed of a plurality of layers. An intermediate layer such as a white background adjusting layer, a charge adjusting layer, an adhesive layer, a primer layer, or an undercoat layer may be formed between the support and the heat insulating layer. When the intermediate layer is included, the receiving layer, the heat insulating layer, and the intermediate layer can be formed by simultaneous multilayer coating. In addition, a release layer may be formed on the outermost layer on the surface that is overlapped with the transfer material.
Furthermore, a curl adjusting layer, a writing layer, and a charge adjusting layer are preferably formed on the back side of the support.

These heat-sensitive transfer image-receiving sheets are prepared by applying a coating solution on a support and drying. In the present invention, the receiving layer and the heat insulating layer are each preferably two layers or more, or one of the two or more layers is a preferred embodiment, but it is more preferable that the layer on the receiving layer side adjacent to the heat insulating layer is coated simultaneously. The layer on the receiving layer side may be a receiving layer or an intermediate layer having other functions.
Hereinafter, this process will be described in detail.

(Application)
Many coating methods are known. Examples include dip coating, air knife coating, blade coating, forward roll coating, reverse roll coating, gravure coating, rod coating, spin coating, slot coating, curtain coating, and slide coating. Among these, curtain coating and slide coating are methods in which the coating film thickness is determined by the flow rate of liquid delivered by a pump or the like, and simultaneous multilayer coating is possible.
In the production of the thermal transfer image-receiving sheet, it can be used by appropriately selecting from the above methods, but since a uniform coating film thickness can be obtained and simultaneous multilayer coating is possible, curtain coating and slide Application is preferably used in the present invention.
As an apparatus for the slide coating method, there is a multilayer slide bead apparatus proposed by Russell et al. In US Pat. No. 2,761,791. This device forms a bead in the gap where a plurality of coating liquids flowing down the slide surface meet the support that is continuously running at the tip of the slide surface, and the coating liquid is applied to the support surface via the bead. To do. Therefore, it is important for this type of apparatus to be able to form beads stably. An example of the shape of a slide coater is Stephen F. et al. Kistler, Petert. It is also described in “LIQUID FILM COATING” written by Schweizer (CHAPMAN & HALL, 1997).
Curtain coating is a method of coating a support that runs continuously at a constant speed under a free-falling liquid film. There are several methods such as an extrusion type and a slide type. In the slide type coater, the multilayer liquid film created on the slide surface falls freely from the slide end. Therefore, the shape of the slide surface is devised so that a falling liquid film is smoothly formed.

In order to feed a coating solution prepared so that the physical properties such as liquid concentration, viscosity, surface tension, pH, etc. are appropriate values, it is necessary to continuously carry out while removing bubbles and foreign substances. is there.
Various methods are conceivable for continuously supplying the coating liquid at a constant flow rate, but it is preferable to use a metering pump from the viewpoint of accuracy and reliability. Examples include a plunger pump and a diaphragm pump. In the diaphragm type, the plunger and the liquid to be sent are separated by the two diaphragms, and the operation of the plunger is transmitted to the liquid to be sent via the drive oil and the pure water between the two diaphragms. It is done. Variations in the flow rate of the liquid feed pump lead to variations in the coating film thickness, and sufficient accuracy is required.

When it is necessary to reduce the influence of the pump pulsation, an auxiliary device for absorbing the pulsation is used. Some methods are known, and a pipeline type pulsation absorbing device can be cited as an example (Japanese Patent Laid-Open No. 1-255793).
In order to remove foreign matter, it is preferable to filter the coating solution. Various kinds of filter media can be used, and a cartridge filter medium can be given as an example. In use, it is preferable to treat in advance in order to prevent air retained in the pores of the filter medium from being mixed into the coating liquid in the form of bubbles. Although several methods are known, as an example, treatment with a liquid containing a surfactant or the like (US Pat. No. 5,096,602) can be mentioned.

  Along with foreign matter, bubbles also cause coating surface failure. For this reason, it is preferable to defoam and defoam bubbles that are mixed in the coating liquid and foams that are floating on the liquid surface. As a technique for this purpose, there is separation of bubbles from liquid or dissolution of bubbles in liquid. As separation methods, vacuum defoaming, ultrasonic defoaming, centrifugal defoaming and the like are known. Examples of the method for dissolving in a liquid include ultrasonic pipeline defoaming.

  When using an additive that deteriorates the aging stability of the coating solution by adding it to the coating solution, in order to shorten the aging time from adding to coating, A method of adding just before is known. Such a method can also be adopted in the present invention. As a mixer for this purpose, there are a static mixer and a dynamic mixer.

The slide bead coating apparatus mainly includes a coating head and a backup roller that wraps and supports a continuously running support. Inside the block that forms the coating head, there is formed a liquid pool that spreads the coating liquid fed from the liquid feeding line in the width direction of the support, and a narrow slit communicates with this liquid pool up to the slide surface. An opening is formed. This slide surface is formed on the upper surface of the coating head and is inclined downward toward the backup roller side.
The coating liquid supplied to each liquid reservoir is pushed out from each slit to the slide surface, and sequentially overlaps while flowing down the slide surface to form a multilayer coating film. To reach. The coating liquid that has reached the tip forms a coating liquid bead in the gap between the tip and the support surface that is wound around the backup roller and travels, and is applied to the support surface via the coating liquid bead. The lower part is depressurized to stabilize the bead. Therefore, a decompression chamber is formed below the backup roller. The decompression chamber serves to stabilize the bead by setting the lower side of the bead to a negative pressure and to make it easier for excess coating liquid not applied to the web to flow down into the decompression chamber.

  The start of coating is performed by moving the coating head from the standby position to the support side in a state where a laminar flow is formed on the slide surface so that the gap between the coating head and the support is appropriately sized. .

  When a large amount of coating is performed, a bonded support may be used. Since the gap between the coating head and the support is narrow, the bead may be disturbed by a slight step at the joint, resulting in coating failure. There is a method of providing unevenness immediately after joining (Japanese Patent Laid-Open No. 50-43140), or a method for retracting Giesa (Japanese Patent Laid-Open No. 63-80872).

There are two types of curtain coating methods: an extra-rusion type and a slide type. In the extra-trusion type, the coating liquid supplied to the liquid reservoir by the liquid feed pump is extruded from the narrow slit so as to be uniform in the coating width direction. A pair of edge guides are provided at both ends of the slit outlet, and a curtain-like liquid film is formed between them. The liquid film falls freely and collides with a continuously running support to form a coating layer.
In the slide type, a coating head similar to that used for slide bead coating is used, and the coating liquid sent by the pump to the liquid reservoir of the coater is discharged from the narrow slit, falls on the slide surface, and is provided at both ends of the lower end. A curtain-like liquid film is formed between the edge guides. In the case of simultaneous multilayer coating, the coating liquids are stacked without mixing while flowing down the slide surface to form a liquid film. The slide surface is inclined, and the coating liquid flows down on the slide surface by gravity.
There are several methods for starting and stopping the coating. For example, a method of placing a shielding object between the formed curtain film and the support is known. Application is started by removing the shield, and application is stopped by returning to the original position.

(Dry)
After being applied, the coated product is temporarily stored through a set zone (only when cooled and solidified), a drying zone, a humidity control zone, and winding.
The coating solution to which various known gelling agents such as gelatin, pectin, agar, carrageenan, gellan gum and the like are added is gelled and solidified by cooling in the set zone. Water evaporation also occurs at this stage.

In the drying zone, drying proceeds through a constant rate drying period in which the drying speed is constant and the material temperature is substantially equal to the wet bulb temperature, and a decreasing rate drying period in which the drying speed is low and the material temperature increases. In the constant rate drying period, all external heat is used to evaporate moisture. During the rate-decreasing drying period, moisture diffusion inside the material becomes rate-limiting, and the drying rate decreases due to the receding of the evaporation surface, etc., and the applied heat is used for increasing the material temperature.
In the set zone and the drying zone, moisture movement occurs between each coating film and between the support and the coating film, and the coating film is cooled and solidified by moisture evaporation. For this reason, since the history of the film surface temperature, drying time, etc. in the middle of drying greatly affects the quality and performance of the product, it is necessary to set conditions.
In the present invention, in order to define a point until 60% of the total moisture amount is dried, the moisture amount will be described first.
From the heat-sensitive transfer image-receiving sheet cut out from each point in the drying zone, a square of 1 cm x 1 cm is evenly punched in 5 vertical and horizontal locations, and the average value obtained by measuring the moisture content (volatile content) by the absolutely dry method is the drying zone The amount of water at each point. Here, the total amount of water is the amount of water after application and before drying. Specifically, it is the amount of water at the entrance of the drying zone (which also corresponds to the exit of the set zone if a set zone exists). is there. By calculating the difference of the moisture content at each point in the drying zone with respect to the total moisture content and dividing this value by the total moisture content, the percentage is expressed as a percentage. Suppose that it is doing. Next, the transfer time of the thermal transfer image-receiving sheet from the entrance of the drying zone to the point of the drying zone where 60% of the total water content is dried is obtained, and this time is defined as the time until 60% of the total water content is dried.
The film surface temperature at each point in the drying zone may be measured by a contact method using a thermocouple, or by a non-contact surface thermometer.
The film surface temperature needs to be 5 to 20 ° C. until 60% of the total water content is dried, and more preferably 10 to 20 ° C. At a point where 60% or more of the total water content is dried, 5 to 50 ° C is preferable, 5 to 40 ° C is more preferable, and 10 to 35 ° C is more preferable. When the film surface temperature is higher than 20 ° C until 60% of the total moisture content is dry, the viscosity is low, and there is mixing of two adjacent coating solutions for simultaneous multi-layer coating and water movement. , Local viscosity change is expected, resulting in unevenness, resulting in density unevenness during printing, or moisture evaporation from the film surface, so simultaneous multi-layer coating was performed In some cases, the difference in shrinkage between layers may lead to cracks on the coated surface. If the coated surface is cracked, white spots at the time of printing or defective transfer of the protective layer may occur, so it is necessary to reduce cracks on the coated surface.
The drying time is preferably 1 minute or less (preferably 10 seconds or more and 1 minute or less) until 60% of the total water content is dried. The drying time in the present invention is the drying time in the drying zone. Strictly speaking, it is slightly dried in the set zone, but does not include this time.

The dried coated product is adjusted to a certain moisture content and wound up, but the moisture content during winding is affected by the moisture content and temperature during winding and storage of the coated product. It is preferable to set appropriate humidity conditioning process conditions for the rate.
Generally, the dura mater reaction is more likely to proceed under high temperature and high humidity conditions. However, if the moisture content is too high, the coated products may adhere to each other or a problem in performance may occur. For this reason, it is necessary to set appropriately the moisture content (humidity control conditions) and storage conditions of winding.

  As typical drying means, there are an air loop method, a pickling method, and the like. The air loop method is a method in which a dry air jet is blown onto a coated product supported by a roller, and there are a method in which a duct is arranged vertically and a method in which a duct is arranged horizontally. The drying function and the transport function are basically separated, and the degree of freedom such as the air volume is large. However, since many rollers are used, poor conveyance of the base such as slippage, wrinkles, and slips is likely to occur. The spiral winding method is a method in which a coated product is wound around a cylindrical duct in a spiral shape and floated with dry air (air floating), and transported and dried. No. 20438). In addition, there is a drying method in which ducts are installed on the upper and lower sides and conveyed. In general, the dry distribution is better than that of the helical type, but the flying ability is inferior.

Hereinafter, the structure of the thermal transfer image-receiving sheet of the present invention will be described in detail.
(Receptive layer)
The receiving layer functions to receive the dye transferred from the thermal transfer sheet and maintain the formed image. In the heat-sensitive transfer image-receiving sheet of the present invention, the receiving layer contains a polymer latex.
The receiving layer can contain an ultraviolet absorber, a release agent, a lubricant, an antioxidant, an antiseptic, a surfactant, an organic solvent, and other additives.

<Polymer latex>
The polymer latex used in the present invention will be described. In the heat-sensitive transfer image-receiving sheet of the present invention, the polymer latex used in the receptor layer is a dispersion of water-insoluble hydrophobic polymer as fine particles in a water-soluble dispersion medium. As the dispersion state, the polymer is emulsified in a dispersion medium, the emulsion is polymerized, the micelle is dispersed, or the polymer molecule has a partially hydrophilic structure and the molecular chain itself is molecularly dispersed. Anything may be used.
In the present invention, the polymer latex used in the receiving layer is required to have an action of receiving the dye transferred from the thermal transfer sheet, and has the effect of receiving the dye in the receiving layer by this action. Moreover, it can also have a function as a binder for maintaining the layer structure of the receiving layer. The polymer latex used in the receiving layer is obviously different from emulsions and matting agent fine particle dispersions containing hydrophobic additives such as lubricants and antioxidants, which will be described later, in that they have a function of receiving dyes.
For polymer latex, Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Kobunshi Publishing (1978), Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Takashi Published by Molecular Press (1993), Soichi Muroi, “Synthetic Latex Chemistry”, published by High Polymer Press (1970), supervised by Yoshiaki Mitsuzawa, “Development and application of water-based coating materials”, CM Publishing ( 2004) and JP-A-64-538. The average particle size of the dispersed particles is preferably 1 to 50000 nm, more preferably 5 to 1000 nm.
The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

  The polymer latex may be a so-called core / shell type latex in addition to a normal uniform polymer latex. In this case, it may be preferable to change the glass transition temperature between the core and the shell. The glass transition temperature (Tg) of the polymer latex of the present invention is preferably -30 ° C to 130 ° C, more preferably 0 ° C to 120 ° C. Among these, the glass transition temperature is preferably 40 ° C or higher (preferably 40 to 120 ° C), and more preferably 70 ° C or higher (70 to 100 ° C).

  Preferred embodiments of the polymer latex of the present invention include polymer latexes such as acrylic polymers, polyesters, rubbers (for example, SBR resin), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, and polyolefins. Can be preferably used. The polymer latex may be a linear polymer, a branched polymer, a crosslinked polymer, a so-called homopolymer obtained by polymerizing a single monomer, or a copolymer obtained by polymerizing two or more monomers. Good. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of the polymer constituting these polymer latexes is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 in terms of number average molecular weight. If the molecular weight is too small, the mechanical strength of the layer containing the latex is insufficient, and if it is too large, the film formability is poor and this is not preferred. A crosslinkable polymer latex is also preferably used.

  The monomer used for the synthesis of the polymer latex used in the present invention is not particularly limited, and monomers that can be polymerized by a normal radical polymerization or ionic polymerization method are preferably the following monomer groups (a) to (j). Can be used. Polymer monomers can be synthesized by selecting these monomers independently and freely in combination.

-Monomer group (a)-(j)-
(A) Conjugated dienes: 1,3-pentadiene, isoprene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, cyclo Pentadiene and the like.
(B) Olefins: ethylene, propylene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, 4-pentenoic acid, methyl 8-nonenoate, vinylsulfonic acid, trimethylvinylsilane, trimethoxyvinylsilane, 1,4- Divinylcyclohexane, 1,2,5-trivinylcyclohexane, etc.

  (C) α, β-unsaturated carboxylic acid esters: alkyl acrylate (eg, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylate (eg, 2-chloro Ethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, etc.), substituted alkyl methacrylate (eg, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin) Monomethacrylate, 2-acetoxyethyl methacrylate, tetrahydrofurfuryl meta Relate, 2-methoxyethyl methacrylate, polypropylene glycol monomethacrylate (polyoxypropylene added mole number = 2 to 100), 3-N, N-dimethylaminopropyl methacrylate, chloro-3-N, N, N-trimethyl Ammoniopropyl methacrylate, 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc.), unsaturated dicarboxylic acid derivatives (For example, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.), polyfunctional esters (for example, ethylene glycol diacrylate, Tylene glycol dimethacrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2, 4-cyclohexanetetramethacrylate and the like.

(D) Amides of α, β-unsaturated carboxylic acid: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tert-butylacrylamide N-tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetone acrylamide, itaconic acid diamide, N-methylmaleimide, 2 -Acrylamide-methylpropane sulfonic acid, methylene bisacrylamide, dimethacryloyl piperazine and the like.
(E) Unsaturated nitriles: acrylonitrile, methacrylonitrile and the like.
(F) Styrene and derivatives thereof: styrene, vinyl toluene, p-tert-butyl styrene, vinyl benzoic acid, methyl vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-hydroxymethyl styrene, p -Styrene sulfonic acid sodium salt, p-styrene sulfinic acid potassium salt, p-aminomethylstyrene, 1,4-divinylbenzene and the like.
(G) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether, and the like.
(H) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, and the like.
(I) α, β-unsaturated carboxylic acid and salts thereof: acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate and the like.
(J) Other polymerizable monomers: N-vinylimidazole, 4-vinylpyridine, N-vinylpyrrolidone, 2-vinyloxazoline, 2-isopropenyloxazoline, divinylsulfone, and the like.

  The polymer latex that can be used in the present invention is commercially available, and the following polymers can be used. Examples of the acrylic polymer include Sebian A-4635, 4718, 4601 manufactured by Daicel Chemical Industries, Ltd., Nipol Lx811, 814, 821, 820, 855 manufactured by Nippon Zeon Co., Ltd. (P-17: Tg 36 ° C.), 857 × 2 (P-18: Tg 43 ° C.), Voncoat R3370 (P-19: Tg 25 ° C.), 4280 (P-20: Tg 15 ° C.) manufactured by Dainippon Ink & Chemicals, Jurimer ET-410 (manufactured by Nippon Pure Chemical Co., Ltd.) P-21: Tg44 ° C), AE116 (P-22: Tg50 ° C) manufactured by JSR Corporation, AE119 (P-23: Tg55 ° C), AE121 (P-24: Tg58 ° C), AE125 (P-25: Tg60) ° C), AE134 (P-26: Tg48 ° C), AE137 (P-27: Tg48 ° C), AE140 (P-28: Tg53 ° C) ), AE173 (P-29: Tg 60 ° C.), Toagosei Co., Ltd. Aron A-104 (P-30: Tg 45 ° C.), Takamatsu Yushi Co., Ltd. NS-600X, NS-620X, Nissin Chemical Industry ( Vinibrand 2580, 2583, 2641, 2770, 2770H, 2635, 2886, 5202C, 2706, etc. manufactured by Co., Ltd. (all are trade names).

  Examples of polyesters include: FINETENX ES650, 611, 675, 850 manufactured by Dainippon Ink Chemical Co., Ltd., WD-size, WMS manufactured by Eastman Chemical, A-110, A-115GE manufactured by Takamatsu Yushi Co., Ltd., A- 120, A-21, A-124GP, A-124S, A-160P, A-210, A-215GE, A-510, A-513E, A-515GE, A-520, A-610, A-613, A-615GE, A-620, WAC-10, WAC-15, WAC-17XC, WAC-20, S-110, S-110EA, S-111SL, S-120, S-140, S-140A, S- 250, S-252G, S-250S, S-320, S-680, DNS-63P, NS-122L, NS-122LX, NS-244LX NS-140L, NS-141LX, NS-282LX, Aronmelt PES-1000 series, PES-2000 series, Toyobo Co., Ltd. Bironal MD-1100, MD-1200, MD-1220, MD-1245 MD-1250, MD-1335, MD-1400, MD-1480, MD-1500, MD-1930, MD-1985, and Sephorjon ES manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of polyurethanes include HYDRAN AP10, AP20, AP30, AP40, 101H, Vonic 1320NS, 1610NS, manufactured by Dainippon Ink and Chemicals, Inc., D-1000, D-2000, D-6000, manufactured by Dainichi Seika Co., Ltd. Examples include D-4000, D-9000, NS-155X, NS-310A, NS-310X, NS-311X manufactured by Takamatsu Yushi Co., Ltd., and Elastron manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (all trade names).

  Examples of rubbers include LACSTAR 7310K, 3307B, 4700H, 7132C (manufactured by Dainippon Ink and Chemicals), Nipol Lx416, LX410, LX430, LX435, LX110, LX415A, LX438C, 2507H, LX303A, LX407BP series, V1004, MH5055 (manufactured by Nippon Zeon Co., Ltd.) and the like (all are trade names).

  As an example of polyvinyl chloride, Nippon Zeon Co., Ltd. G351, G576, Nissin Chemical Industry Co., Ltd. Vinibrand 240, 270, 277, 375, 386, 609, 550, 601, 602, 630, 660, 671, 683, 680, 680S, 681N, 685R, 277, 380, 381, 410, 430, 432, 860, 863, 865, 867, 900, 900GT, 938, 950, etc. (all are trade names). Examples of polyvinylidene chlorides include L502 and L513 manufactured by Asahi Kasei Kogyo Co., Ltd., D-5071 manufactured by Dainippon Ink and Chemicals, Inc. (all are trade names). Examples of polyolefins include Chemipearl S120, SA100, V300 (P-40: Tg 80 ° C.) manufactured by Mitsui Petrochemical Co., Ltd., Voncoat 2830, 2210, 2960 manufactured by Dainippon Ink Chemical Co., Ltd., Sumitomo Seika Co., Ltd. Examples of Zyxen, Sepoljon G, and copolymerized nylons include Sepoljon PA manufactured by Sumitomo Seika Co., Ltd. (all are trade names).

  Examples of the polyvinyl acetates include Nishin Chemical Industry Co., Ltd., Vinibrand 1080, 1082, 1085W, 1108W, 1108S, 1563M, 1566, 1570, 1588C, A22J7-F2, 1128C, 1137, 1138, A20J2, A23J1, A23J1, A23K1, A23P2E, A68J1N, 1086A, 1086D, 1086D, 1108S, 1187, 1241LT, 1580N, 1083, 1571, 1572, 1581, 4465, 4466, 4468W, 4468S, 4470, 4485LL, 4495LL, 1023, 1042, 1060, 1060S, 1080M, 1084W, 1084S, 1096, 1570K, 1050, 1050S, 3290, 1017AD, 1002, 1006, 1008, 107L, 1225,1245L, GV-6170, GV-6181,4468W, such as 4468S, and the like (all trade names).

  These polymer latexes may be used alone or in combination of two or more as required. The polymer latex of the present invention may be any one or any combination of vinyl chloride / acrylic compound copolymer latex, vinyl chloride / vinyl acetate copolymer latex, vinyl chloride / vinyl acetate / acrylic compound copolymer latex. Preferably, vinyl chloride / acrylic compound copolymer latex is most preferable.

  In the present invention, since the polymer latex used in the receiving layer is preferably dispersed in a water-soluble dispersion medium, at least one layer is coated with an aqueous coating solution, but has a plurality of receiving layers. In this case, it is preferable to prepare all these receiving layers by applying an aqueous coating solution and then drying. However, “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water. Components other than water in the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxyethyl phenyl ether A water miscible organic solvent such as can be used.

  The minimum film-forming temperature (MFT) of the polymer latex is preferably −30 ° C. to 90 ° C., more preferably about 0 ° C. to 70 ° C.

  Preferable examples of the polymer latex used in the present invention include polylactic acid esters, polyurethanes, polycarbonates, polyesters, polyacetals, SBRs, and polyvinyl chlorides. Among these, polyesters, polycarbonates Most preferably, polyvinyl chlorides are included.

In the present invention, among the above polymer latexes, polyvinyl chlorides are preferred in the present invention. Among the polyvinyl chlorides, that is, the polymer latex containing at least a repeating unit obtained from vinyl chloride, a polymer latex containing 50 mol% or more of a repeating unit obtained from the vinyl chloride is preferable, and a copolymerized polymer latex is more preferable. It is. As such a copolymer latex, a monomer copolymerized with vinyl chloride is preferably acrylic or methacrylic acid or an ester thereof, vinyl acetate or ethylene, more preferably acrylic or methacrylic acid or an ester thereof, and an acrylic ester. Is more preferable. The alcohol part of the ester part of the acrylate ester preferably has 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms.
Examples of such polyvinyl chlorides include those mentioned above, among others, Viniblanc 240, Vinibrand 270, Vinibrand 276, Vinibrand 277, Vinibrand 375, Vinibrand 380, Vinibrand 386, Vinibrand 410, Vinibrand 430, Vinibrand 432, VINYBRAN 550, VINYBRAN 601, VINYBRAN 602, VINYBRAN 609, VINYBRAN 619, VINYBRAN 680, VINYBRAN 680S, VINYBRAN 681N, VINYBRAN 683, VINYBRAN 685R, VINYBRAN 690, VINYBRAN 860, VINYBRAN 863, VINYBRAN 685, VINYBRAN 867, VINYBRAN 900, , ViniBran 950 (all are Nissin Chemical Industry Co., Ltd., SE1320, S-830 (all are Sumitomo Chemtech ( )) Is preferable.

The polymer latex used in the present invention is used for receiving the dye transferred from the thermal transfer sheet, but any polymer may be used in combination with the polymer latex.
The polymer that can be used in combination may be used for receiving a dye, but may also be used as a binder for holding the polymer latex.
Such polymers are preferably transparent or translucent and colorless, and are natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, and other media forming films such as gelatins, polyvinyl alcohols, hydroxys. Ethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl pyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymers, styrene -Acrylonitrile copolymers, styrene-butadiene copolymers, polyvinyl acetals (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resins, poly salts Vinylidene, polyepoxides, polycarbonates, polyvinyl acetates, polyolefins, and polyamides. The binder may be coated from water or an organic solvent or emulsion.

  In addition to the polymer latex used for the purpose of accepting the dye migrating from the ink sheet, when using a polymer latex mainly used as the binder, the polymer latex has processing brittleness and image storage stability. The glass transition temperature (Tg) is preferably in the range of -30 ° C to 70 ° C, more preferably in the range of -10 ° C to 50 ° C, still more preferably in the range of 0 ° C to 40 ° C. It is also possible to use a blend of two or more polymers as the binder, and in this case, it is preferable that the weighted average Tg in consideration of the composition falls within the above range. Moreover, when phase-separating or having a core-shell structure, the weighted average Tg is preferably within the above range.

This glass transition temperature (Tg) can be estimated by calculating with the following equation.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature value (Tgi) of each monomer may be the value of “Polymer Handbook (3rd Edition)” (by J. Brandrup, EH Immergut (Wiley-Interscience, 1989)).
In addition, although the glass transition temperature of the said polymer latex for receiving the dye in this invention and the hollow polymer mentioned later is prescribed | regulated by a measured value, it is also possible to estimate with said calculation method.

<Water-soluble polymer>
In the present invention, it is one of preferred embodiments that the receiving layer contains a water-soluble polymer.
Here, the water-soluble polymer is a polymer that dissolves 0.05 g or more with respect to 100 g of water at 20 ° C., preferably 0.1 g or more, more preferably 0.5 g or more, and particularly preferably 1 g or more. Is. The polymer latex described above is obtained by dispersing polymer fine particles in a dispersion medium, and is different from the water-soluble polymer of the present invention.
Water-soluble polymers that can be used in the present invention include natural polymers (polysaccharides, microorganisms, animals), semi-synthetic polymers (cellulose, starch, alginic acid), and synthetic polymers (vinyl, Other).
In the present invention, a water-soluble polymer is sometimes referred to as a water-soluble binder in order to distinguish it from the polymer latex.

Of the water-soluble polymers that can be used in the present invention, natural polymers and semi-synthetic polymers will be described in detail. Examples of plant polysaccharides include gum arabic, κ-carrageenan, ι-carrageenan, λ-carrageenan, guar gum (such as Supercol manufactured by Squalon), locust bean gum, pectin, tragacanth, and corn starch (Purity- manufactured by National Starch & Chemical Co.). 21), phosphorylated starch (National Star & Chemical Co., National 78-1898, etc.), and other microbial polysaccharides such as xanthan gum (Kelco, Keltrol T), dextrin (National Star & Chemical Co., Nadex 360, etc.) ) And other animal-based natural polymers such as gelatin (Crodine B419 from Croda), casein Such as sodium chondroitin sulfate (such as Croda made Cromoist CS), and the like (all trade names). Cellulose-based materials include ethyl cellulose (ICF Cellofas WLD, etc.), carboxymethyl cellulose (Daicel CMC, etc.), hydroxyethyl cellulose (Daicel HEC, etc.), hydroxypropyl cellulose (Aqualon Klucel, etc.), and methyl cellulose (Henkel). Viscontran, etc.), nitrocellulose (Isopropyl Wet, etc. from Hercules), cationized cellulose (Crodacel QM, etc. from Croda), etc. (all are trade names). As starch systems, phosphorylated starch (such as National Star &Chemical's National 78-1898), alginic acid systems such as sodium alginate (such as Kelco's Keltone), propylene glycol alginate, and other classifications include cationized guar gum (Alcolac). Hi-care 1000, etc.) and sodium hyaluronate (Hyalure, etc. from Lifecare Biomedical) (all are trade names).
In the present invention, gelatin is one of the preferred embodiments. The gelatin used in the present invention may have a molecular weight of 10,000 to 1,000,000. The gelatin used in the present invention may contain anions such as Cl ⁻ and SO ₄ ²⁻ , and may contain cations such as Fe ²⁺ , Ca ²⁺ , Mg ²⁺ , Sn ²⁺ and Zn ^2+. . It is preferable to add gelatin dissolved in water.

  Of the water-soluble polymers that can be used in the present invention, synthetic polymers will be described in detail. Examples of the acrylic system include sodium polyacrylate, polyacrylic acid copolymer, polyacrylamide, polyacrylamide copolymer, polydiethylaminoethyl (meth) acrylate quaternary salt or a copolymer thereof, and the vinyl system includes polyvinylpyrrolidone, Polyvinyl pyrrolidone copolymer, polyvinyl alcohol, etc. include polyethylene glycol, polypropylene glycol, polyisopropyl acrylamide, polymethyl vinyl ether, polyethylene imine, polystyrene sulfonic acid or copolymer thereof, naphthalene sulfonic acid condensate salt, polyvinyl sulfonic acid Or a copolymer thereof, polyacrylic acid or a copolymer thereof, acrylic acid or a copolymer thereof, a maleic acid copolymer, a maleic acid monoester copolymer, an acryloylme Propane sulfonic acid or its copolymer, etc.), polydimethyldiallylammonium chloride or its copolymer, polyamidine or its copolymer, polyimidazoline, dicyanciamide condensate, epichlorohydrin-dimethylamine condensate, polyacrylamide Hoffman Decomposition product, water-soluble polyester (Plus Coat Z-221, Z-446, Z-561, Z-450, Z-565, Z-850, Z-3308, RZ-105, RZ-570, manufactured by Kyodo Chemical Co., Ltd.) , Z-730, RZ-142 (both are trade names)).

Further, it has a superabsorbent polymer described in US Pat. No. 4,960,681, JP-A-62-245260, etc., that is, —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal). A homopolymer of vinyl monomers or a copolymer of these vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H (trade name) manufactured by Sumitomo Chemical Co., Ltd.) is also used. Can do.

Of the water-soluble polymers comprising synthetic polymers that can be used in the present invention, polyvinyl alcohols are preferred.
Hereinafter, polyvinyl alcohol will be described in more detail.
As a complete saponified product, PVA-105 [polyvinyl alcohol (PVA) content 94.0% by mass or more, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.5% by mass or less, volatile content 5 0.0 mass% or less, viscosity (4 mass%, 20 ° C.) 5.6 ± 0.4 CPS], PVA-110 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, acetic acid Sodium content 1.5% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 11.0 ± 0.8 CPS], PVA-117 [PVA content 94.0% by mass, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.0 mass%, volatile content 5.0 mass%, viscosity (4 mass%, 20 ° C.) 28.0 ± 3.0 CPS],

PVA-117H [PVA content 93.5% by mass, saponification degree 99.6 ± 0.3 mol%, sodium acetate content 1.85% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 29.0 ± 3.0 CPS], PVA-120 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 39.5 ± 4.5 CPS], PVA-124 [PVA content 94.0 mass%, saponification degree 98.5 ± 0.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 60.0 ± 6.0 CPS],

PVA-124H [PVA content 93.5% by mass, saponification degree 99.6 ± 0.3 mol%, sodium acetate content 1.85% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 61.0 ± 6.0 CPS], PVA-CS [PVA content 94.0% by mass, saponification degree 97.5 ± 0.5 mol%, sodium acetate content 1.0% by mass, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 27.5 ± 3.0 CPS], PVA-CST [PVA content 94.0 mass%, saponification degree 96.0 ± 0.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 27.0 ± 3.0 CPS], PVA-HC [PVA content 90.0 mass%, saponification degree 99. 85 mol% or more, sodium acetate content 2.5 mass%, volatile content 8.5 mass%, viscosity (4 quality %, 20 ℃) 25.0 ± 3.5CPS] (or more, both of Kuraray Co., Ltd., trade name of) such as,

As a partially saponified product, PVA-203 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4 mass%, 20 ° C.) 3.4 ± 0.2 CPS], PVA-204 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0 mass %, Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 3.9 ± 0.3 CPS], PVA-205 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 Mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 5.0 ± 0.4 CPS],

PVA-210 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 9.0 ± 1.0 CPS], PVA-217 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 22.5 ± 2.0 CPS], PVA-220 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 30.0 ± 3.0 CPS],

PVA-224 [PVA content 94.0% by mass, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 44.0 ± 4.0 CPS], PVA-228 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 65.0 ± 5.0 CPS], PVA-235 [PVA content 94.0 mass%, saponification degree 88.0 ± 1.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 95.0 ± 15.0 CPS],

PVA-217EE [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 23.0 ± 3.0 CPS], PVA-217E [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 23.0 ± 3.0 CPS], PVA-220E [PVA content 94.0 mass%, saponification degree 88.0 ± 1.0 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 31.0 ± 4.0 CPS],

PVA-224E [PVA content 94.0% by mass, saponification degree 88.0 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20% ° C) 45.0 ± 5.0 CPS], PVA-403 [PVA content 94.0 mass%, saponification degree 80.0 ± 1.5 mol%, sodium acetate content 1.0 mass%, volatile content 5. 0 mass%, viscosity (4 mass%, 20 ° C.) 3.1 ± 0.3 CPS], PVA-405 [PVA content 94.0 mass%, saponification degree 81.5 ± 1.5 mol%, sodium acetate contained 1.0 mass%, volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 4.8 ± 0.4 CPS],

PVA-420 [PVA content 94.0% by mass, saponification degree 79.5 ± 1.5 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass], PVA-613 [PVA-containing Rate 94.0% by mass, saponification degree 93.5 ± 1.0 mol%, sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 16.5 ± 2.0 CPS], L-8 [PVA content 96.0 mass%, saponification degree 71.0 ± 1.5 mol%, sodium acetate content 1.0 mass% (ash content), volatile content 3.0 mass% , Viscosity (4% by mass, 20 ° C.), 5.4 ± 0.4 CPS] (all are trade names manufactured by Kuraray Co., Ltd.).

  In addition, said measured value is calculated | required according to JISK-6726-1977.

  As for the modified polyvinyl alcohol, those described in Koichi Nagano et al., “Poval” (published by Kobunshi Shuppankai) are used. There is modification by cation, anion, -SH compound, alkylthio compound, silanol.

  As such modified polyvinyl alcohol (modified PVA), C polymer as C-118, C-318, C-318-2A, C-506 (all are trade names manufactured by Kuraray Co., Ltd.), HL polymer HL-12E, HL-1203 (all are trade names made by Kuraray Co., Ltd.), HM polymer is HM-03, HM-N-03 (all are trade names made by Kuraray Co., Ltd.), KL-118, KL-318, KL-506, KM-118T, KM-618 (all are trade names manufactured by Kuraray Co., Ltd.) as the K polymer, and M-115 (manufactured by Kuraray Co., Ltd.) as the M polymer. (Trade name), MP-102, MP-202, MP-203 (all are trade names made by Kuraray Co., Ltd.) as MP polymers, and MPK-1, MPK- as MPK polymers. , MPK-3, MPK-4, MPK-5, MPK-6 (all are trade names manufactured by Kuraray Co., Ltd.), R-1130, R-2105, R-2130 (all are all as R polymers) Kuraray Co., Ltd. product name), V polymer V-2250 (Kuraray Co., Ltd. product name) and the like.

  Polyvinyl alcohol can be adjusted in viscosity or stabilized by a small amount of solvent or inorganic salt added to the aqueous solution. For details, refer to the above document, Koichi Nagano et al., “Poval”, Polymer Publications published by the publisher, pages 144 to 154 can be used. As a typical example, it is possible to improve the coating surface quality by containing boric acid, which is preferable. The addition amount of boric acid is preferably 0.01 to 40% by mass with respect to polyvinyl alcohol.

  In the present invention, the water-soluble polymer contained in the receiving layer (and / or the heat insulating layer) is preferably polyvinyl alcohols or gelatin, and most preferably gelatin. The addition amount of the water-soluble polymer in the receiving layer is preferably 1 to 25% by mass, and more preferably 1 to 10% by mass with respect to the entire receiving layer. It is also one of preferred embodiments that a water-soluble polymer is contained in a layer other than the receptor layer without using a water-soluble polymer in the receptor layer.

The method for synthesizing the polymer latex used in the present invention will be described below.
As a method for synthesizing the polymer latex, an emulsion polymerization method obtained as a latex is most preferable. Also preferred is a method of preparing a polymer in a solution and neutralizing or adding an emulsifier and then adding water and forcibly stirring to prepare an aqueous dispersion.

  In the emulsion polymerization method, for example, water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) is used as a dispersion medium, and the monomer is 5 to 150% by mass with respect to the dispersion medium. Using the mixture and the total amount of monomers, an emulsifier and a polymerization initiator are used, and polymerization is carried out with stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 24 hours. Various conditions such as the dispersion medium, the monomer concentration, the initiator amount, the emulsifier amount, the dispersant amount, the reaction temperature, and the monomer addition method are appropriately set in consideration of the type of monomer used. Moreover, it is preferable to use a dispersing agent as needed.

  The emulsion polymerization method can be generally performed according to the following literature. Tadashi Okuda, Hiroshi Inagaki, “Synthetic Resin Emulsion”, published by Polymer Press (1978), Takaaki Sugimura, Akio Kataoka, Junichi Suzuki, Keiji Kasahara, “Application of Synthetic Latex”, Published by Polymer Press (1993) 1), Soichi Muroi, “Chemistry of Synthetic Latex”, published by Kobunshi Shuppankai (1970). In the emulsion polymerization method for synthesizing the polymer latex used in the present invention, a batch polymerization method, a monomer (continuous / divided) addition method, an emulsion addition method, a seed polymerization method, etc. can be selected from the viewpoint of latex productivity. A batch polymerization method, a monomer (continuous / divided) addition method, and an emulsion addition method are preferred.

  The polymerization initiator only needs to have radical generating ability, and may be an inorganic peroxide such as persulfate or hydrogen peroxide, a peroxide described in “Oil peroxide catalog” of Nippon Oil & Fats, and Wako Jun. The azo compounds described in Yaku Kogyo Co., Ltd. “Azo Polymerization Initiator Catalog” can be used. Among them, water-soluble peroxides such as persulfate and water-soluble azo compounds described in Wako Pure Chemical Industries, Ltd. “Azo Polymerization Initiator Catalog” are preferable. Ammonium persulfate, sodium persulfate, potassium persulfate, Azobis (2-methylpropionamidine) hydrochloride, azobis (2-methyl-N- (2-hydroxyethyl) propionamide), azobiscyanovaleric acid is more preferable, and in particular, ammonium persulfate, sodium persulfate, potassium persulfate, etc. Peroxides are preferred from the viewpoints of image storability, solubility, and cost.

  As the addition amount of the polymerization initiator, the polymerization initiator is preferably 0.3% by mass to 2.0% by mass, and 0.4% by mass to 1.75% by mass with respect to the total amount of monomers. Is more preferable, and 0.5% by mass to 1.5% by mass is particularly preferable.

  As the polymerization emulsifier, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but the anionic surfactant has dispersibility and image storability. From the viewpoint, it is preferable to use a sulfonic acid type anionic surfactant because polymerization stability can be ensured in a small amount and resistance to hydrolysis, and a long chain represented by Perex SS-H (trade name, Kao Corporation). Alkyl diphenyl ether disulfonate is more preferable, and a low electrolyte type such as Pionein A-43-S (trade name, Takemoto Yushi Co., Ltd.) is particularly preferable.

  As the polymerization emulsifier, a sulfonic acid type anionic surfactant is preferably used in an amount of 0.1% by mass to 10.0% by mass with respect to the total amount of monomers, and 0.2% by mass to 7.5% by mass is used. It is more preferable that 0.3% by mass to 5.0% by mass is used.

  In the synthesis of the polymer latex used in the present invention, it is preferable to use a chelating agent. The chelating agent is a compound capable of coordinating (chelating) multivalent ions such as metal ions such as iron ions and alkaline earth metal ions such as calcium ions. Japanese Patent Publication No. 6-8956, US Pat. -73645, JP-A-4-127145, JP-A-4-247703, JP-A-4-305572, JP-A-6-11805, JP-A-5-1773312, JP-A-5-66527, JP-A-5-67527. 158195, JP-A-6-118580, JP-A-6-110168, JP-A-6-161054, JP-A-6-175299, JP-A-6-214352, JP-A-7-114161, JP-A-7-114154 JP-A-7-120894, JP-A-7-199433, JP-A-7-306504, JP-A-9-43792 , JP-A-8-314090, JP-A-10-182571, JP-A-10-182570, can be employed compounds described in JP-A-11-190892.

  Examples of the chelating agent include inorganic chelate compounds (sodium tripolyphosphate, sodium hexametaphosphate, sodium tetrapolyphosphate, etc.), aminopolycarboxylic acid chelate compounds (nitrilotritriacetic acid, ethylenediaminetetraacetic acid, etc.), organic phosphonic acid chelate compounds ( Research Disclosure 18170, JP-A-52-102726, 53-42730, 56-97347, 54-121127, 55-4024, 55-4025, 55-29883, 55 -126241, 55-65955, 55-65956, 57-17943, 54-61125, and West German Patent No. 1045373), polyphenol-based chelating agents, polyamine-based chelates Preferably such DOO compounds, with aminopolycarboxylic acid derivatives being particularly preferred.

  Preferable examples of the aminopolycarboxylic acid derivatives include the compounds listed in the appendix of “EDTA (-Complexane Chemistry)” (Nanedo, 1977), and some of the carboxyl groups of these compounds are sodium or potassium. Alkali metal salts and ammonium salts such as may be substituted. Particularly preferred aminocarboxylic acid derivatives include iminodiacetic acid, N-methyliminodiacetic acid, N- (2-aminoethyl) iminodiacetic acid, N- (carbamoylmethyl) iminodiacetic acid, nitrilotriacetic acid, ethylenediamine-N, N '-Diacetic acid, ethylenediamine-N, N'-di-α-propionic acid, ethylenediamine-N, N'-di-β-propionic acid, N, N'-ethylene-bis (α-o-hydroxyphenyl) glycine N, N′-di (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-diacetic acid-N, N′-diacethydroxamic acid, N-hydroxyethylethylenediamine-N , N ′, N′-triacetic acid, ethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,2-propylenediamine-N, N, N ′, N′-tetraacetic acid, d l-2,3-diaminobutane-N, N, N ′, N′-tetraacetic acid, meso-2,3-diaminobutane-N, N, N ′, N′-tetraacetic acid, 1-phenylethylenediamine-N , N, N ′, N′-tetraacetic acid, d, l-1,2-diphenylethylenediamine-N, N, N ′, N′-tetraacetic acid, 1,4-diaminobutane-N, N, N ′, N'-tetraacetic acid, trans-cyclobutane-1,2-diamine-N, N, N ', N'-tetraacetic acid, trans-cyclopentane-1,2-diamine-N, N, N', N'- Tetraacetic acid, trans-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cis-cyclohexane-1,2-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane -1,3-diamine-N, N, N ′, N′-tetraacetic acid, cyclohexane-1,4-diamine-N, N N ′, N′-tetraacetic acid, o-phenylenediamine-N, N, N ′, N′-tetraacetic acid, cis-1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, trans -1,4-diaminobutene-N, N, N ′, N′-tetraacetic acid, α, α′-diamino-o-xylene-N, N, N ′, N′-tetraacetic acid, 2-hydroxy-1 , 3-propanediamine-N, N, N ′, N′-tetraacetic acid, 2,2′-oxy-bis (ethyliminodiacetic acid), 2,2′-ethylenedioxy-bis (ethyliminodiacetic acid), ethylenediamine -N, N'-diacetic acid-N, N'-di-α-propionic acid, ethylenediamine-N, N'-diacetic acid-N, N'-di-β-propionic acid, ethylenediamine-N, N, N ', N'-tetrapropionic acid, diethylenetriamine-N, N, N ′, N ″, N ″ -pentaacetic acid, triethylenetetra -N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, 1,2,3-triaminopropane-N, N, N ′, N ″, N ″ Examples include ', N' ''-hexaacetic acid, and those obtained by substituting some of the carboxyl groups of these compounds with alkali metal salts such as sodium and potassium, and ammonium salts.

  The addition amount of the chelating agent is preferably 0.01% by mass to 0.4% by mass, more preferably 0.02% by mass to 0.3% by mass with respect to the total amount of monomers. It is especially preferable that it is 03 mass%-0.15 mass%. When the amount of the chelating agent is less than 0.01% by mass, capture of metal ions mixed in the production process of the polymer latex becomes insufficient, stability against aggregation of the latex is lowered, and applicability is deteriorated. On the other hand, if it exceeds 0.4%, the viscosity of the latex increases and the coatability is lowered.

  A chain transfer agent is preferably used for the synthesis of the polymer latex used in the present invention. As the chain transfer agent, those described in “Polymer Handbook, 3rd edition” (Wiley-Interscience, 1989) are preferable. Sulfur compounds are more preferred because they have high chain transfer ability and can be used in small amounts. Hydrophobic mercaptan-based chain transfer agents such as tert-dodecyl mercaptan and n-dodecyl mercaptan are particularly preferred.

  The amount of the chain transfer agent is preferably 0.2% by mass to 2.0% by mass, more preferably 0.3% by mass to 1.8% by mass, and 0.4% by mass to 1.6% by mass with respect to the total amount of monomers. Mass% is particularly preferred.

  In emulsion polymerization, in addition to the above compounds, electrolytes, stabilizers, thickeners, antifoaming agents, antioxidants, vulcanizing agents, antifreezing agents, gelling agents, vulcanization accelerators, etc. are described in synthetic rubber handbooks, etc. These additives may be used.

  In the polymer latex used in the present invention, an aqueous solvent can be used as a solvent in the coating solution, but a water-miscible organic solvent may be used in combination. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide. The amount of these organic solvents added is preferably 40% or less, more preferably 30% or less of the solvent.

The polymer latex used in the present invention preferably has a polymer concentration of 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 55% by mass with respect to the latex liquid.
The addition amount of the polymer latex is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, based on the total polymer content in the receptor layer.
In addition, the polymer latex in the image receiving sheet of the present invention includes a gel or a dried film state formed by drying a part of the solvent after coating.

<Organic solvent>
In the present invention, an organic solvent having a boiling point of 140 to 220 ° C. may be used in the coating solution for the constituent layer coated on the receiving layer side on the support. It is preferable that the polymer latex has an action of forming a film. The organic solvent may be added to any of the coating liquids of the constituent layers coated on the receiving layer side on the support, but is preferably present at least in the receiving layer. It is most preferable that it is contained in a coating solution for coating this receiving layer.
Examples of the organic solvent that can be added to the coating solution for producing the thermal transfer image-receiving sheet include ethyl acetoacetate, tetramethylsulfone, γ-butyllactone, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, diacetone alcohol, diglyme, Dimethyl sulfoxide, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol-n-butyl acetate, cyclohexanone, cyclopentanone, lactic acid Ethyl, methyl lactate, butyl acetate, acetic acid Chlohexyl, 2-heptanone, ethyl pyruvate, 3,5,5-trimethyl-2-cyclohexen-1-one, butyl lactate, propylene glycol, propylene glycol diacetate, propylene glycol-n-propyl ether acetate, propylene glycol phenyl ether Acetate, propylene glycol monomethyl ether acetate, 2-ethylhexyl acetate, 3-methoxy-3-methylbutyl acetate, tripropylene glycol methyl ethyl acetate, 1-methoxypropyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, tetrahydrofuryl alcohol, ethoxypropyl propionate and the like can be mentioned.

In the present invention, the organic solvent includes a plasticizer in the case where the polymer latex to be used contains a plasticizer, an auxiliary for adding the polymer latex, and a dispersion auxiliary used in the emulsified dispersion described later. Also included are those used as a solvent for forming the heat insulating layer, but as described above, it is preferably added to the coating solution for the receiving layer, more preferably added as a solvent.
The organic solvent of the present invention has a boiling point of 140 to 220 ° C., and when an organic solvent having a boiling point of 140 ° C. or lower is used, the strength of the receiving layer cannot be made uniform, and scratches in the output image are caused. The effect of preventing the occurrence is small. In the case of an organic solvent having a boiling point of 140 ° C. or higher, the above-mentioned failure prevention effect is further increased. When an organic solvent having a boiling point of 220 ° C. is used, the strength of the receiving layer can be made uniform and failure can be prevented, but bleeding of the printed image occurs and the image quality deteriorates.
The boiling point of the organic solvent is preferably 150 to 220 ° C, more preferably 170 to 220 ° C, and further preferably 180 to 220 ° C. In particular, in the present invention, when compared with an organic solvent used merely as a film-forming aid, many of these organic solvents have insufficient film-forming action or films after producing a thermal transfer image-receiving sheet. Disadvantages that cause adverse effects (deterioration of color bleeding, etc.) due to remaining in the resin are eliminated, and at the same time, the effect of the present invention is effectively exerted.
The organic solvent is preferably a water-soluble organic solvent, preferably 50 g or more dissolved in 100 ml of water, that is, one that is mixed without layer separation, and more preferably 100 g or more dissolved in 100 ml of water. On the other hand, the composition of the organic solvent preferably has 4 or more (preferably 12 or less) carbon atoms, more preferably 5 or more (preferably 10 or less). Further, the organic solvent is preferably composed of carbon atoms, hydrogen atoms and oxygen atoms or / and sulfur atoms, more preferably composed of carbon atoms, hydrogen atoms and oxygen atoms. is there. The organic solvent is preferably neutral, not acidic or alkaline. When viewed as a functional group constituting an organic solvent, it has at least a hydroxyl group and / or an alkyleneoxy group (preferably —CH ₂ O—, —CH ₂ CH ₂ O—).

  Examples of such organic solvents include alcohol solvents, ethylene glycol solvents, propylene glycol solvents, and diethylene glycol solvents, and those in which these hydroxyl groups are etherified and esterified can be mentioned. For example, ethylene glycol (197.2 ° C), propylene glycol (187.3 ° C), butyl cellosolve (171.2 ° C), methyl cellosolve acetate (144.5 ° C), cellosolve acetate (156.3 ° C), methylcarb Thor (193.2 ° C.), carbitol (201.9 ° C.), diethyl carbitol (186.0 ° C.), carbitol acetate (218.0 ° C.), diacetone alcohol (168.0 ° C.).

These organic solvents may be disadvantageous in terms of dispersion stability of the polymer latex in the state of the coating liquid containing the polymer latex in the property of promoting the film formation of the latex to be used. It is necessary to select an appropriate one.
Moreover, in order to improve the dispersion stability of the polymer latex in the coating solution, a method of mixing an organic solvent with the coating solution immediately before coating during coating feeding can also be suitably used.
The addition amount of the organic solvent is preferably 1% or more and 100% or less, more preferably 3% or more and 80% or less, and still more preferably 10% or more with respect to the solid content of the latex polymer of the receiving layer. 60% or less. In addition, also when adding to another layer, it is preferable to add by mass ratio with the solid content of the said polymer latex in a receiving layer.
The organic solvent is preferably one that volatilizes at the time of coating, drying, and further storage, either immediately after the production of the thermal transfer image-receiving sheet or on the support of the thermal transfer image-receiving sheet either after production or until image formation. It is 3% or less (preferably 1% or less) with respect to the total coating solid content (mass) in all the constituent layers on the receiving layer side. If it remains 3% or more, blurring of the printed image occurs, resulting in a problem in that the image quality deteriorates. In order to make such a residual amount, in addition to the conditions in the drying process and the drying process that is normally performed, heat treatment for this purpose may be performed, but the drying process that is normally performed It is preferable to achieve this.
Moreover, the aspect which is 0.001%-3% of the content and residual amount of said organic solvent, and the aspect which is 0 to less than 0.001% (mode which does not contain substantially) are preferable.

<Ultraviolet absorber>
In the present invention, an ultraviolet absorber may be added to the receiving layer in order to improve light resistance. At this time, the UV absorber can be fixed to the receiving layer by increasing the molecular weight, and can be prevented from being diffused into the ink sheet or sublimation / transpiration due to heating.
As the ultraviolet absorber, compounds having various ultraviolet absorber skeletons widely known in the field of information recording can be used. Specific examples include 2-hydroxybenzotriazole type ultraviolet absorbers, 2-hydroxybenzotriazine type ultraviolet absorbers, and compounds having a 2-hydroxybenzophenone type ultraviolet absorber skeleton. A compound having a benzotriazole type or triazine skeleton is preferable from the viewpoint of ultraviolet absorption ability (absorption coefficient) / stability, and a compound having a benzotriazole type or benzophenone type skeleton is preferable from the viewpoint of increasing the molecular weight or forming a latex. Specifically, an ultraviolet absorber described in JP 2004-361936 A can be used.

  The ultraviolet absorber preferably has absorption in the ultraviolet region and does not have an absorption edge in the visible region. Specifically, when added to the receiving layer to form a thermal transfer image-receiving sheet, the reflection density at 370 nm is preferably Abs 0.5 or more, and the reflection density at 380 nm is more preferably Abs 0.5 or more. . The reflection density at 400 nm is preferably Abs 0.1 or less. A high reflection density in the range exceeding 400 nm is not preferable because the image is yellowed.

  In the present invention, the ultraviolet absorber has a high molecular weight and preferably has a mass average molecular weight of 10,000 or more, more preferably a mass average molecular weight of 100,000 or more. As a means for increasing the molecular weight, it is preferable to graft an ultraviolet absorber onto the polymer. The polymer that becomes the main chain preferably has a polymer skeleton that is inferior in dyeability to the dye used in combination. Moreover, it is preferable to have sufficient film strength when the film is formed. The graft ratio of the ultraviolet absorber to the polymer main chain is preferably 5 to 20% by mass, and more preferably 8 to 15% by mass.

Moreover, it is more preferable that the polymer grafted with the ultraviolet absorber is made into a latex. The receptor layer can be formed by forming an aqueous dispersion type coating solution into a latex to form a latex, and the manufacturing cost can be reduced. For example, the method described in Japanese Patent No. 3450339 can be used as a method for forming a latex. Examples of the latex-made ultraviolet absorber include ULS-700, ULS-1700, ULS-1383MA, ULS-1635MH, XL-7016, ULS-933LP, ULS-935LH, Shin-Nakamura Chemical Co., Ltd. Commercially available ultraviolet absorbers such as New Coat UVA-1025W, New Coat UVA-204W, and New Coat UVA-4512M (both are trade names) can also be used.
When the polymer to which the ultraviolet absorber is grafted is made into a latex, it is possible to form a receiving layer in which the ultraviolet absorber is uniformly dispersed by mixing with the latex of the above-mentioned dyeable receiving polymer and applying it.

  The added amount of the polymer grafted with the ultraviolet absorber or the latex thereof is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to the dyeable accepting polymer latex forming the receptor layer.

<Release agent>
In addition, a release agent can be added to the receiving layer in order to prevent thermal fusion with the heat-sensitive transfer sheet during image formation. As the release agent, silicone oil and phosphoric ester plasticizer fluorine compound can be used, and silicone oil is particularly preferably used. As the silicone oil, modified silicone oils such as epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, and polyether modification are preferably used. The reaction product of vinyl modified silicone oil and hydrogen modified silicone oil is good. The addition amount of the release agent is preferably 0.2 to 30 parts by mass with respect to the receiving polymer.
The lubricant described in the emulsion section below is almost synonymous with the same effect as the release agent described here. In this invention, what was used as a dispersion for convenience was made into the mold release agent demonstrated here as a lubricant emulsion and the other thing.

<Emulsions>
Hydrophobic additives such as lubricants and antioxidants can be added to the layers of the image receiving sheet (for example, receiving layer, heat insulating layer, intermediate layer, lower layer) by a known method such as the method described in US Pat. No. 2,322,027. In the coating layer). In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476 No. 4,599,296, JP-B-3-62256, or a high boiling point organic solvent described in the specification or the like, if necessary, in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C. Can be used. These lubricants, antioxidants, high-boiling organic solvents and the like can be used in combination of two or more.
Examples of the lubricant include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder; silicone oil, phosphate ester compounds, fluorine surfactants, silicone surfactants, and other in the technical field. A known release agent can be used. Silicone compounds such as various waxes, fluorine compounds represented by fluorine surfactants, silicone surfactants, silicone oils and / or cured products thereof are preferably used.

<Surfactant>
In the heat-sensitive transfer image-receiving sheet of the present invention, a surfactant can be contained in the above arbitrary layer. Among these, it is preferable to make it contain in a receiving layer and an intermediate | middle layer.
The addition amount of the surfactant is preferably 0.01 to 5% by mass, more preferably 0.01 to 1% by mass, and 0.02 to 0.2% by mass with respect to the total solid content. It is particularly preferred that Various surfactants such as anionic, nonionic, and cationic surfactants are known. As the surfactant that can be used in the present invention, known ones can be used. For example, those introduced in “Supervision of Functional Surfactant / Mitsuo Tsunoda, Issued / August 2000, Chapter 6”. Among them, an anionic fluorine-containing surfactant is preferable. Application is possible even when no surfactant is contained, but since the surface tension of the application liquid is high, the application surface may be uneven and uneven. By containing a surfactant in the coating solution, the surface tension can be lowered, unevenness during coating can be eliminated, the coated surface can be made uniform, and coating can be performed stably.

  Although the specific example of a fluorine compound is illustrated below, the fluorine compound which can be used by this invention is not restrict | limited at all by the following specific examples. Unless otherwise specified, the alkyl group and perfluoroalkyl group in the structure notation of the following exemplified compounds means a group having a linear structure.

  These fluorine compounds are used as a surfactant in a coating composition for forming a layer constituting a heat-sensitive transfer image-receiving sheet (in particular, a receiving layer, a heat insulating layer, an intermediate layer, an undercoat layer, a back layer, etc.). However, in the present invention, it can be preferably contained in the receiving layer and the intermediate layer.

<Matting agent>
In the present invention, it is preferable to add a matting agent for imparting releasability. The matting agent is preferably contained in the outermost surface layer, the layer functioning as the outermost surface layer of the heat-sensitive transfer image-receiving sheet, or a layer close to the outer surface. The outermost surface layer can be made into two layers as required. Most preferably, it is added to the outermost receiving layer. The matting agent can be added to both the outermost layer on the image forming layer surface and the outermost layer on the back surface, and can also be added to both layers. In particular, it is preferable to include a matting agent on the side of the support containing the slip agent.

  The matting agent is preferably dispersed in advance with a binder and used as a matting agent particle dispersion.

  Examples of the matting agent generally include fine particles of an organic compound insoluble in water and fine particles of an inorganic compound. In the present invention, fine particles containing an organic compound are preferable from the viewpoint of dispersibility. As long as it contains an organic compound, it may be an organic compound fine particle composed of an organic compound alone, or an organic / inorganic composite fine particle containing not only an organic compound but also an inorganic compound. Examples of the matting agent include, for example, U.S. Pat. Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782, 3,539,344, Those well known in the silver salt sensitive material industry such as the organic matting agent described in each specification such as US Pat. No. 3,767,448 can be used.

  Since the temperature of the receiving layer surface becomes high during image printing, the matting agent preferably has heat resistance. In particular, a polymer having a thermal decomposition temperature of 200 ° C. or higher is preferable. More preferably, it is a polymer having a thermal decomposition temperature of 240 ° C. or higher. In addition, when the image is printed, not only heat but also pressure is applied to the surface of the receiving layer, so that the matting agent is preferably hard.

  The matting agent contained in the outermost layer on the image forming layer side and the outermost layer adjacent layer is dispersed in advance with a binder and used as a matting agent particle dispersion. The dispersion method is (a) a matting agent. The dispersion of the matting agent by removing the low boiling point organic solvent from the emulsion by emulsifying and dispersing the polymer to be dissolved in an aqueous medium as a solution (for example, dissolved in a low boiling point organic solvent) to obtain polymer droplets There are two methods: (b) a method in which fine particles such as a polymer to be a matting agent are prepared in advance, and a dispersion is prepared so as not to cause lumps in an aqueous medium. In the present invention, in consideration of the environment, the method (b) in which a low-boiling organic solvent is not discharged to the environment is preferable.

  Since the dispersion state of the mat particle dispersion in the present invention is stabilized when it contains a surfactant, it is preferable to add a surfactant.

<Preservative>
When a coating solution, a thermal transfer image-receiving sheet, a print image, and the like are stored, microorganisms (particularly bacteria, mold, yeast, etc.) adhere to these materials during storage, and their performance is often lowered. In order to prevent this, a preservative can be contained in a range that does not affect other performances.
The preservative referred to in the present invention is a compound used to suppress the compound used in the thermal transfer image-receiving sheet from undergoing a decomposition reaction due to the growth of the microorganism, and the definition by the general formula and the specific compound are: It is described in Hogaku Handbook, Gihodo Publishing (1986), Hiroshi Horiguchi, Antifungal Chemistry, Sankyo Publishing (1986), Encyclopedia of Antifungal and Antifungal, Published by the Japanese Society of Antifungal and Antimicrobial (1986). .
The preservative contained in the heat-sensitive transfer image-receiving sheet of the present invention is not particularly limited, but phenol or derivatives thereof, formalin, imidazole derivatives, sodium dehydroacetate, 4-isothiazolin-3-one derivatives, benzoisothiazoline-3-one , Benzotriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, derivatives of pyrozine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, 2-mercaptopyridine-N-oxide or salts thereof, formaldehyde donor antibacterial agents Etc. Among these, phenol or a derivative thereof, 4-isothiazolin-3-one derivative, benzisothiazolin-3-one, and the like are preferable.

  In addition to these, compounds represented by any one of the following general formulas [I] to [IV] can be used as preservatives.

一般式〔Ｉ〕中、Ｒ_１、Ｒ_２は同じでも異なっていてもよく、水素原子、ヒドロキシ基、又は低級アルキル基を表す。Ｘは水素原子、ハロゲン原子、ニトロ基、シアノ基、アリール基、低級アルキル基、低級アルケニル基、アラルキル基、アルコキシ基、−ＣＯＲ_３、−ＳＯ_２Ｒ_４、又は−Ｎ（Ｒ_５）Ｒ_６を表し、Ｒ_３、Ｒ_４は水素原子、−ＯＭ、低級アルキル基、低級アルコキシ基、又は−Ｎ（Ｒ_７）Ｒ_８を表す。
Ｒ_５、Ｒ_６は同じでも異なっていてもよく、水素原子、低級アルキル基、−ＣＯＲ_９、又は−ＳＯ_２Ｒ_１０を表わす。Ｒ_９、Ｒ_１０は低級アルキル基、又は−Ｎ（Ｒ_１１）Ｒ_１２を表し、Ｒ_７、Ｒ_８、Ｒ_１１、Ｒ_１２は同じであっても異なっていてもよく水素原子又は低級アルキル基を表す。
Ｍは、水素原子、アルカリ金属原子又は１価のカチオンを形成するに必要な原子群を表わし、ｌは２〜６の整数を表し、ｍは１〜４までの整数を表し、ｎは６−ｍの整数を表す。ただし、Ｒ_１、Ｒ_２、Ｘが複数存在する時はそれぞれが互いに異なっていてもよい。

In general formula [I], R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, a hydroxy group, or a lower alkyl group. X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an aryl group, a lower alkyl group, a lower alkenyl group, an aralkyl group, an alkoxy group, —COR ₃ , —SO ₂ R ₄ , or —N (R ₅ ) R _6. R ₃ and R ₄ represent a hydrogen atom, —OM, a lower alkyl group, a lower alkoxy group, or —N (R ₇ ) R ₈ .
R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, a lower alkyl group, —COR ₉ , or —SO ₂ R ₁₀ . R ₉ and R ₁₀ represent a lower alkyl group or —N (R ₁₁ ) R ₁₂ , and R ₇ , R ₈ , R ₁₁ , and R ₁₂ may be the same or different, and may be a hydrogen atom or a lower alkyl group. Represents.
M represents a hydrogen atom, an alkali metal atom, or an atomic group necessary to form a monovalent cation, l represents an integer of 2 to 6, m represents an integer of 1 to 4, and n represents 6- represents an integer of m. However, when there are a plurality of R ₁ , R ₂ , and X, each may be different from each other.

一般式〔ＩＩ〕中、Ｒ_１３は水素原子、アルキル基、アルケニル基、アラルキル基、アリール基、複素環基、

In the general formula [II], R ₁₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group,

を表し、Ｒ_１４、Ｒ_１５は各々水素原子、アルキル基、アリール基、シアノ基、複素環基、アルキルチオ基、アルキルスルホキシ基、アルキルスルホニル基を表し、Ｒ_１４とＲ_１５は互いに結合して芳香環を形成していても良い。
Ｒ_１６、Ｒ_１７は各々水素原子、アルキル基、アリール基、アラルキル基を表す。これらの中でも、Ｒ_１４、Ｒ_１５が水素原子であり、Ｒ_１３がメチル基であるもの（以下、化合物ＩＩ−ａと称する）が好ましい。また、Ｒ_１４とＲ_１５が互いに結合して芳香環を形成しＲ_１３が水素原子であるものと化合物ＩＩ−ａとの組み合わせ、および、Ｒ_１４が塩素原子、Ｒ_１５が水素原子、Ｒ_１３がメチル基であるものと化合物ＩＩ−ａとの組み合わせはさらに好ましい。

R ₁₄ and R ₁₅ each represent a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group, or an alkylsulfonyl group, and R ₁₄ and R ₁₅ are bonded to each other. An aromatic ring may be formed.
R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Among these, those in which R ₁₄ and R ₁₅ are hydrogen atoms and R ₁₃ is a methyl group (hereinafter referred to as compound II-a) are preferable. In addition, R ₁₄ and R ₁₅ are bonded to each other to form an aromatic ring and R ₁₃ is a hydrogen atom in combination with Compound II-a, and R ₁₄ is a chlorine atom, R ₁₅ is a hydrogen atom, R ₁₃ The combination of the compound in which is a methyl group and compound II-a is further preferred.

一般式〔ＩＩＩ〕中、Ｒ_１８は水素原子、アルキル基、ヒドロキシメチル基を表わし、Ｒ_１９は水素原子、アルキル基を表す。

一般式〔ＩＶ〕式中、Ｒ_２０は低級アルキレン基を表し、Ｘは水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、シアノ基、低級アルキル基、低級アルコキシ基、−ＣＯＲ_２１、−Ｎ（Ｒ_２２）Ｒ_２３、−ＳＯ_３Ｍを表し、Ｒ_２１は水素原子、−ＯＭ、低級アルキル基、アリール基、アラルキル基、低級アルコキシ基、アリールオキシ基、アラルキルオキシ基、−Ｎ（Ｒ_２４）Ｒ_２５を表す。
Ｒ_２２、Ｒ_２３は各々水素原子、低級アルキル基、アリール基、アラルキル基、−ＣＯＲ_２６、−ＳＯ_２Ｒ_２６を表し、互に同じであっても異なっていてもよく、Ｒ_２４、Ｒ_２５は各々水素原子、低級アルキル基、アリール基、アラルキル基を表わし、互に同じであっても異なっていてもよく、Ｒ_２６は低級アルキル基、アリール基、アラルキル基を表わし、Ｍは水素原子、アルカリ金属原子及び１価のカチオンを形成するに必要な原子群を表し、ｐは０または１を表わし、ｑは０または１から５までの整数を表わす。

In the general formula [III], R ₁₈ represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R ₁₉ represents a hydrogen atom or an alkyl group.

In the general formula [IV], R ₂₀ represents a lower alkylene group, X represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, a lower alkoxy group, —COR ₂₁ , —N (R ₂₂ ) represents R ₂₃ , —SO ₃ M, R ₂₁ represents a hydrogen atom, —OM, lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group, —N (R ₂₄ ) R ₂₅ .
R ₂₂ and R ₂₃ each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, —COR ₂₆ , —SO ₂ R _{26, and} may be the same or different from each other, and R ₂₄ , R ₂₅ Each represents a hydrogen atom, a lower alkyl group, an aryl group or an aralkyl group, and may be the same or different from each other, R ₂₆ represents a lower alkyl group, an aryl group or an aralkyl group, M represents a hydrogen atom, An atomic group necessary for forming an alkali metal atom and a monovalent cation is represented, p represents 0 or 1, and q represents 0 or an integer from 1 to 5.

  Any one of the preservatives may be used alone, or two or more arbitrary compounds may be selected and used in combination. The preservative may be added as it is, but it may be dissolved in water or an organic solvent such as methanol, ethanol, isopropyl alcohol, acetone, ethylene, ethylene glycol, and added as a solution to the thermal transfer image-receiving sheet coating solution. Or you may add in latex. Alternatively, it may be dissolved in a high boiling point solvent, a low boiling point solvent, or a mixed solvent of both, and then emulsified and dispersed in the presence of a surfactant and added to the latex.

<Hardener>
The hardener used in the present invention as a crosslinking agent can be added to a coating layer (for example, a receiving layer, a heat insulating layer, a subbing layer, etc.) of a thermal transfer image-receiving sheet.
Examples of the hardening agent that can be used in the present invention include H-1,4,6,8,14 on page 17 of JP-A-1-214845, column 13 to U.S. Pat. No. 4,618,573. 23 compounds (H-1 to 54) represented by formulas (VII) to (XII), compounds (H-1 to 76) represented by formula (6) on page 8, lower right of JP-A-2-214852, In particular, H-14 and the compounds described in claim 1 of US Pat. No. 3,325,287 are preferably used. Examples of hardeners are US Pat. No. 4,678,739, column 41, US Pat. No. 4,791,042, JP-A Nos. 59-116655, 62-245261, and 61-18842. And the hardening agent described in JP-A-4-218444 or the specification thereof. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N′-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid, or polymer hardeners (compounds described in JP-A-62-234157). Preferably, a vinyl sulfone type hardener and chlorotriazines are used.
More preferable hardeners in the present invention are compounds represented by the following general formula (A) or (B).
Formula (A)
_{(CH 2 = CH-SO 2} ) n-L
General formula (B)
(X—CH ₂ —CH ₂ —SO ₂ ) nL
In general formulas (A) and (B), X represents a halogen atom, and L represents an n-valent organic linking group. When the compound represented by formula (A) or (B) is a low molecular compound, n represents an integer of 1 to 4. In the case of a polymer compound, L is an organic linking group containing a polymer chain, and n is in the range of 10 to 1000.

  In general formulas (A) and (B), X is preferably a chlorine atom or a bromine atom, more preferably a bromine atom. n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably an integer of 2 to 3, and most preferably 2.

  L represents an n-valent organic group, preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups are ether bond, ester bond, amide bond, sulfonamide bond, urea bond, It may be further connected with a urethane bond or the like. These groups may have a substituent, such as a halogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, alkoxycarbonyl. Groups, carbamoyloxy groups, acyl groups, acyloxy groups, acylamino groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups, phosphoryl groups, carboxyl groups, sulfo groups, etc., halogen atoms, alkyl groups, hydroxy groups, Alkoxy groups, aryloxy groups and acyloxy groups are preferred.

  These hardeners can be obtained by referring to the method described in US Pat. No. 4,173,481.

As the chlorotriazine hardener, a 1,3,5-triazine compound in which at least one chloro atom is substituted at the 2-position, 4-position or 6-position is preferable.
More preferably, the chlorine atom is substituted at the 2nd, 4th or 6th position by 2 or 3 groups. At least one chlorine atom may be substituted at the 2-position, 4-position or 6-position, and a group other than a chlorine atom may be substituted at the remaining positions. Examples of these groups include a hydrogen atom, a bromine atom, Fluorine atom, iodine atom, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group, heterocyclic group, hydroxy group, nitro group, cyano group, amino group, hydroxylamino group, alkylamino group, Arylamino group, heterocyclic amino group, acylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, alkoxy group, alkenoxy group, aryloxy group, heterocyclic oxy group, acyl group, acyloxy group, alkyl Or arylsulfonyl group, alkyl or arylsulfinyl group, alkyl Ku is arylsulfonyloxy group, a mercapto group, an alkylthio group, an alkenylthio group, an arylthio group, a heterocyclic thio group, such as alkyloxy or aryloxy carbonyl group.
Specific examples of chlorotriazine hardeners include 4,6-dichloro-2-hydroxy-1,3,5-triazine or its Na salt, 2-chloro-4,6-diphenoxytriazine, 2-chloro. -4,6-bis [2,4,6-trimethylphenoxy] triazine, 2-chloro-4,6-diglycidoxy-1,3,5-triazine, 2-chloro-4- (n-butoxy) -6 Glycidoxy-1,3,5-triazine, 2-chloro-4- (2,4,6-trimethylphenoxy) -6-glycidoxy-1,3,5-triazine, 2-chloro-4- (2-chloroethoxy ) -6- (2,4,6-trimethylphenoxy) 1,3,5-triazine, 2-chloro-4- (2-bromoethoxy) -6- (2,4,6-trimethylphenoxy) -1, 3,5-tri 2-chloro-4- (2-di-n-butylphosphatoethoxy) -6- (2,4,6-trimethylphenoxy) -1,3,5-triazine, 2-chloro-4- (2 -Di-n-butylphosphatoethoxy) -6- (2,6-xylenoxy) -1,3,5-triazine and the like, but not limited thereto.
Such a compound can be easily produced by reacting cyanuric chloride (that is, 2,4,6-trichlorotriazine) with a hydroxy compound, a thio compound or an amino compound corresponding to a substituent on the heterocyclic ring.

  These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of water-soluble polymer.

<Antifoaming agent>
The antifoaming agent used in the present invention is present on the surface of the liquid instead of the causative agent of foaming, and itself has an action of imparting a repulsive force that resists thinning of the foam film. Means no compound. Specific examples include alcohols, ethers, polyols, fatty acid esters, metal soaps, phosphate esters, silicones, and nonionic surfactants. Of the commercially available antifoaming agents and compounds having these structures, those having an antifoaming effect can be used alone or in combination or as a mixture.

(A) Alcohols C1-C10 fatty acid alcohol, for example, methanol, ethanol, butanol, octinol, 2-ethylhexanol, etc. can be mentioned.
However, fatty acid alcohols having 1 to 3 carbon atoms need to be added in an amount of 1% or more in order to express the effect clearly, and may swell latex or hollow polymer or the like to promote aggregation. The fatty acid alcohol is preferred.
(B) Fatty acid esters Isoamyl stearate, succinic acid diester, sorbitan lauric acid monoester, sorbitan oleic acid monoester, sorbitan oleic acid triester, oxyethylene sorbitan lauric acid monoester, diethylene glycol distearate, or low molecular weight polyethylene glycol Examples include oleic acid esters.
(C) Ethers Monophenyl ether of ethylene glycol (for example, di-t-diaminophenoxyethanol), dialkyl ether of ethylene glycol (for example, 3-heptyl cellosolve or nonyl cellosolve), dialkyl ether of diethylene glycol (for example, 3-heptyl) Carbitol) and the like, and as commercially available products, for example, Bionine K-17 (manufactured by Takemoto Yushi Co., Ltd.) or Nopco DF122-NS (manufactured by San Nopco Co., Ltd.) can be used.
(D) Polyols There can be mentioned compounds (for example, polyethers) having many alkylene oxide groups (especially ethylene oxide groups) in their structure, and these compounds are excellent in dispersion stability in water. So it has excellent antifoaming effect in the liquid. Examples of commercially available polyether antifoaming agents include Adeka Pluronic series and Adecanol series LG-109, LG-121, LG-294, LG-297 [Asahi Denka Kogyo Co., Ltd.], or SN deformer. 157, 247, 375, 470 [San Nopco Co., Ltd.] can be used.
(E) Metal soaps Various organic acid metal salts can be used, and examples thereof include naphthenic acid metal soaps, synthetic acid metal soaps, and stearic acid metal soaps. Specifically, an aluminum stearate etc. can be mentioned, A naphthenate, a dicnate, or a stearate (all are Dainippon Ink Chemical Co., Ltd. product) etc. can be mentioned.

(F) Silicones An oil type, a compound type, a self-emulsifying type, or an emulsion type silicone antifoaming agent can be mentioned. Particularly, the oil type includes a methyl group in addition to a silicone oil having a general dimethylpolysiloxane structure. Examples of the modified silicone oil may include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, heterofunctional group-modified, polyether-modified, methyl There may be mentioned modified silicone oils such as styryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid content, or fluorine modification. As commercially available products, SH200 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KF96, KS604, KI-6702 (manufactured by Shin-Etsu Silicone Co., Ltd.), SN deformer 5016 (manufactured by San Nopco Co., Ltd.), SH5500 as the compound type. , SC5540 (manufactured by Toray Dow Corning Silicone Co., Ltd.), as a self-emulsifying type BY28-503 (manufactured by Toray Dow Corning Silicone Co., Ltd.), KS508, KS530, KS-538 (manufactured by Shin-Etsu Silicone Co., Ltd.), emulsion type SM5511, SM5512, SM5515 (made by Toray Dow Corning Silicone Co., Ltd.), KM72, KM73, KM98 (made by Shin-Etsu Silicone Co., Ltd.), etc. SF5417 as mino modification, SF8411 and SF8413 as epoxy modification, BY16-880 as carboxyl modification, FS1265 as fluorine modification (all manufactured by Toray Dow Corning Silicone Co., Ltd.), KF-6017 (manufactured by Shin-Etsu Silicone Co., Ltd.) as polyether modification ), FORM BAN MS-575 (manufactured by Ultra Additives Inc.) containing alkyl-modified silicone and polyether modification, and KF-6001 and KF-6003 (manufactured by Shin-Etsu Silicone Co., Ltd.) can be exemplified as carbinol modification.
(G) Nonionic surfactants The following examples can be given.
(1) an alkyl aryl ether ethylene oxide adduct,
_{(2): HO- (C 2 H 4 O} ) n - (C 3 H 6 O) m - (C 2 H 4 O) n -OH
A compound having a molecular weight of 500 to 10,000 and a C ₂ H ₄ O content of 0 to 55%,
(3) Formula: R ¹ (R ² ) CHCOO (C ₂ H ₄ O) n
(Wherein R ¹ and R ² are alkyl groups having 1 to 15 carbon atoms, and n is 1 to 8). R ¹ and R ² each preferably have 5 or more carbon atoms, and more preferably 10 or more.
(4) Acetylene diols and their 0 to 8 mol adducts of ethylene oxide.

  As an antifoamer used by this invention, it can use individually or in combination of 2 or more types or as a mixture.

  Among the antifoaming agents (A) to (G) above, when used for defoaming the coating liquid containing the polymer latex of the present invention and the hollow polymer described later, (F) silicone changes the viscoelasticity of the film, Adhesion with heat-sensitive transfer sheet may be promoted. (G) Nonionic surfactants are difficult to use, for example, the effect is temperature-dependent and the effect is not exhibited unless the temperature of the coating solution is strictly controlled. There are drawbacks, and the antifoaming agents (A) to (E) above are preferred for use in the present invention. As the amount used, the antifoaming effect is exhibited, and the polymer latex and the aggregation of the hollow polymer are not manifested. Furthermore, 0.01 to 5% is preferable, and 0.1 to 1% is more preferable.

The coating amount of the receiving layer is preferably 0.5 to 10 g / m ² (in terms of solid content, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified). The thickness of the receiving layer is preferably 1 to 20 μm.

(Insulation layer)
The heat insulating layer (porous layer) serves to protect the support from heat during heat transfer using a thermal head. Moreover, since it has high cushioning properties, a thermal transfer image-receiving sheet with high printing sensitivity can be obtained even when paper is used as the support.

In the heat-sensitive transfer image-receiving sheet of the present invention, the heat insulating layer contains a hollow polymer.
The hollow polymer in the present invention is a polymer particle having independent pores inside the particle, preferably a polymer latex. For example, 1) water is contained in a partition wall formed of polystyrene, acrylic resin, styrene-acrylic resin, or the like. Non-foamed hollow polymer particles in which the water inside the particles evaporates outside the particles after coating and drying, and the inside of the particles becomes hollow. 2) Low-boiling liquids such as butane and pentane are added to polyvinylidene chloride, poly It is covered with a resin made of acrylonitrile, polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof. After coating, the low-boiling liquid inside the particles expands by heating, and the interior becomes hollow. Foaming type microballoons 3) Microvalves obtained by heating and foaming the above 2) in advance to form a hollow polymer Such as emissions, and the like.

The average particle diameter of these hollow polymers is preferably 0.3 to 1.0 μm. If this size is too small, the hollowness tends to decrease and the desired heat insulating property cannot be obtained. If the size is too large, the frequency of occurrence of planar failures other than coarse particles in the heat insulating layer increases.
The hollow polymer preferably has a hollow ratio of about 20 to 70%, particularly preferably 20 to 50%. If the hollow ratio is too small, the desired heat insulating property cannot be obtained, and if it is too large, the ratio of hollow polymer particles and incomplete hollow particles that are easily broken increases, resulting in printing defects and insufficient film strength. .
Two or more types of hollow polymers can be mixed and used as necessary. Specific examples of 1) include Low and Haas Ropaque 1055, Dainippon Ink Boncoat PP-1000, JSR SX866 (B), Nippon Zeon Nipol MH5055 (all trade names), and the like. . Specific examples of 2) include F-30 and F-50 (both trade names) manufactured by Matsumoto Yushi Seiyaku Co., Ltd. Specific examples of 3) include F-30E manufactured by Matsumoto Yushi Seiyaku Co., Ltd., EXPANSEL 461DE, 551DE, and 551DE20 (all trade names) manufactured by Nippon Ferrite Co., Ltd. The hollow polymer used for the heat insulating layer may be made into a latex.

  The glass transition temperature (Tg) of the hollow polymer is not particularly limited, but is preferably 70 ° C. or higher, and more preferably 100 ° C. or higher. Two or more types of hollow polymers can be mixed and used as necessary.

  The heat insulating layer containing the hollow polymer preferably contains a water-dispersed resin or a water-soluble resin as a binder in addition to the hollow polymer. Examples of the binder resin used in the present invention include acrylic resins, styrene-acrylic copolymers, polystyrene resins, polyvinyl alcohol resins, vinyl acetate resins, ethylene-vinyl acetate copolymers, vinyl chloride vinyl acetate copolymers, and styrene. Known resins such as a butadiene copolymer, a urethane resin, a polyvinylidene chloride resin, a cellulose derivative, casein, starch, and gelatin can be used. These are preferably water-soluble polymers described in the receiving layer. Among these binder resins, gelatin, polyvinyl alcohol, styrene-butadiene copolymer and urethane resin are preferable, and gelatin and polyvinyl alcohol are more preferable. These resins can be used alone or in combination.

The solid content of the hollow polymer in the heat insulating layer is preferably between 5 and 2000 parts by mass when the solids content of the binder resin is 100 parts by mass. Moreover, 1-70 mass% is preferable, and, as for the mass ratio which solid content of a hollow polymer accounts with respect to a coating liquid, 10-40 mass% is more preferable. If the hollow polymer ratio is too small, sufficient heat insulation cannot be obtained. Tend to occur.
The particle size of the hollow polymer particles is preferably 0.1 to 20 μm, more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm. The hollow polymer is particularly preferably a hollow polymer latex.

0.5-14 mass% is preferable, and, as for the quantity which occupies for the coating liquid of the said binder of a heat insulation layer, 1-6 mass% is especially preferable. The coating amount of the hollow polymer in the heat insulation layer is preferably ^{1~100g / m 2, 5~20g / m} 2 is more preferable.
The thickness of the heat insulating layer containing the hollow polymer is preferably 5 to 50 μm, and more preferably 5 to 40 μm.
In the present invention, it is one of preferred embodiments to contain a water-soluble polymer in the heat insulating layer. As the water-soluble polymer, those described above can be used.

(Middle layer)
An intermediate layer may be formed between the receptor layer and the support. For example, a white background adjusting layer, a charge adjusting layer, an adhesive layer, a primer layer, and an undercoat layer are formed. About these layers, it can be set as the structure similar to what was described, for example in patent 3585599, patent 2925244, etc.

(Support)
In the present invention, it is preferable to use a water-resistant support as the support. By using a water-resistant support, it is possible to prevent moisture from being absorbed into the support, and to prevent a change in performance of the receiving layer over time. As the water-resistant support, for example, coated paper or laminated paper can be used. Of these, laminated paper is preferable in terms of surface smoothness. Similar to polyethylene laminated paper (sometimes abbreviated as WP paper) used for photographic paper in the field of silver salt photography, that is, a support mainly composed of cellulose, and at least a receiving layer is applied. A support having a surface coated with a polyolefin resin can be suitably used.

-Coated paper-
The coated paper is a paper obtained by coating various sheets of resin, rubber latex, or polymer material on one side or both sides of a sheet such as a base paper, and the coating amount varies depending on the application. Examples of such coated paper include art paper, cast coated paper, Yankee paper, and the like.

  As the resin applied to the surface of the base paper or the like, it is appropriate to use a thermoplastic resin. Examples of such a thermoplastic resin include the following thermoplastic resins (a) to (h).

(A) Polyolefin resins such as polyethylene resins and polypropylene resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, acrylic resins, and the like.
(B) A thermoplastic resin having an ester bond. For example, a dicarboxylic acid component (these dicarboxylic acid components may be substituted with a sulfonic acid group, a carboxyl group, etc.) and an alcohol component (these alcohol components may be substituted with a hydroxyl group, etc.) Polyester resin, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate and other polyacrylic acid ester resins or polymethacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, styrene -Methacrylic acid ester copolymer resin, vinyl toluene acrylate resin, etc. are mentioned.
Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. it can.
Commercially available products include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130 manufactured by Toyobo Co., Ltd., Tufton NE-382, Tufton manufactured by Kao Corporation U-5, ATR-2009, ATR-2010; Elitel UE3500, UE3210, XA-8153, KZA-7049, KZA-1449 manufactured by Unitika Ltd. Polyester TP-220, R manufactured by Nippon Synthetic Chemical Co., Ltd. -188; various types of thermoplastic resins (all are trade names) of the high loss series manufactured by Seiko Chemical Industry Co., Ltd.

(C) Polyurethane resin etc. are mentioned.
(D) Polyamide resin, urea resin, etc. are mentioned.
(E) Polysulfone resin and the like.
(F) Polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin, and the like.
(G) Cellulose resins, such as polyol resin, ethyl cellulose resin, cellulose acetate resin, etc., such as polyvinyl butyral.
(H) Polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, polyether resin, epoxy resin, phenol resin and the like.
In addition, the said thermoplastic resin may be used individually by 1 type, and may use 2 or more types together.

  Further, the thermoplastic resin may contain pigments or dyes such as brighteners, conductive agents, fillers, titanium oxide, ultramarine blue, and carbon black as required.

-Laminated paper-
The laminated paper is a paper obtained by laminating various resins, rubber or polymer sheets or films on a sheet such as a base paper. Examples of the laminate material include polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, polyimide, triacetyl cellulose, and the like. These resins may be used alone or in combination of two or more.

  In general, the polyolefin is often formed using low density polyethylene, but in order to improve the heat resistance of the support, polypropylene, a blend of polypropylene and polyethylene, high density polyethylene, high density polyethylene and low density polyethylene, It is preferable to use a blend of In particular, it is most preferable to use a blend of high-density polyethylene and low-density polyethylene from the viewpoint of cost, suitability for lamination, and the like.

The blend of the high density polyethylene and the low density polyethylene is used, for example, in a blend ratio (mass ratio) of 1/9 to 9/1. The blend ratio is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3. When forming a thermoplastic resin layer on both surfaces of the support, the back surface of the support is preferably formed using, for example, high-density polyethylene or a blend of high-density polyethylene and low-density polyethylene. The molecular weight of polyethylene is not particularly limited, but the melt index is 1.0 to 40 g / 10 min for both high-density polyethylene and low-density polyethylene and has extrudability. preferable.
In addition, you may perform the process which gives white reflectivity to these sheets or films. Examples of such a treatment method include a method of blending a pigment such as titanium oxide in these sheets or films. This is generally used as a support for photographic paper in the field of silver salt photography (sometimes abbreviated as WP paper).

  The thickness of the support is preferably 25 μm to 300 μm, more preferably 50 μm to 260 μm, and still more preferably 75 μm to 220 μm. Various stiffnesses can be used according to the purpose of the support. As a support for a thermal transfer image-receiving sheet of photographic quality, a support for color silver salt photographic paper is used. Close ones are preferred.

(Curl adjustment layer)
If the support is exposed as it is, the heat-sensitive transfer image-receiving sheet may be curled due to the humidity and temperature in the environment. Therefore, it is preferable to form a curl adjusting layer on the back side of the support. The curl adjusting layer not only prevents the image receiving sheet from curling but also serves as a waterproof. For the curl adjusting layer, polyethylene laminate, polypropylene laminate, or the like is used. Specifically, it can be formed in the same manner as described in, for example, JP-A-61-110135 and JP-A-6-202295.

(Writing layer / Charge adjustment layer)
An inorganic oxide colloid, an ionic polymer, or the like can be used for the writing layer and the charge adjusting layer. As the antistatic agent, for example, a cationic antistatic agent such as a quaternary ammonium salt or a polyamine derivative, an anionic antistatic agent such as an alkyl phosphate, or a nonionic antistatic agent such as a fatty acid ester can be used. . Specifically, for example, it can be formed in the same manner as described in Japanese Patent No. 3585585.

The thermal transfer sheet (ink sheet) used in combination with the above-described thermal transfer image-receiving sheet of the present invention at the time of thermal transfer image formation is provided with a dye layer containing a diffusion transfer dye on a support. Ink sheets can be used. Any conventionally known applying means can be used as the means for applying thermal energy at the time of thermal transfer. For example, the recording time is controlled by a recording device such as a thermal printer (for example, ASK-2000 manufactured by FUJIFILM Corporation). By doing so, the intended purpose can be sufficiently achieved by applying thermal energy of about 0 to 50 mJ / m ² .
The heat-sensitive transfer image-receiving sheet of the present invention can be applied to various uses such as a sheet- or roll-shaped heat-sensitive transfer image-receiving sheet, cards, and transmission-type manuscript preparation sheets capable of thermal transfer recording by appropriately selecting a support. You can also

  The present invention can be used in printers, copiers and the like using a thermal transfer recording system.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. In Examples, “part” or “%” is based on mass unless otherwise specified.

Reference example (preparation of ink sheet)
A polyester film having a thickness of 6.0 μm (Lumirror, trade name, manufactured by Toray Industries, Inc.) was used as a base film. A heat-resistant slip layer (thickness 1 μm) was formed on the back side of the film, and yellow, magenta, cyan composition and protective layer composition having the following composition were applied on the surface side in a single color respectively (coating amount 1 g / m m ² ).
Yellow composition Dye (Macrolex Yellow 6G, trade name, manufactured by Bayer) 5.5 parts by weight Polyvinyl butyral resin 4.5 parts by weight (ESREC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Magenta composition Magenta dye (Disperse Red 60) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) Made by Co., Ltd.)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Cyan composition Cyan dye (Solvent Blue 63) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (ESREC BX-1, trade name, Sekisui Chemical Co., Ltd.) ) Made)
Methyl ethyl ketone / toluene (mass ratio 1/1) 90 parts by mass Protective layer composition 5.5 parts by mass of polyvinyl acetal resin (KS-10, trade name, manufactured by Sekisui Chemical Co., Ltd.)
Colloidal silica (IPA-ST, trade name, manufactured by Nissan Chemical Co., Ltd.) 4 parts by mass Diethyl ketone / isopropyl alcohol (mass ratio 8/2) 90 parts by mass

Example 1
(Preparation of support for thermal transfer image-receiving sheet)
50 parts by mass of LBKP (hardwood bleached kraft pulp) made of acacia and 50 parts by mass of LBKP made of aspen were each beaten to 300 ml of Canadian freeness by a disc refiner to prepare a pulp slurry.
Next, to the pulp slurry obtained above, cation-modified starch (manufactured by Nippon NSC Co., Ltd., trade name, CAT0304L) 1.3%, anionic polyacrylamide (manufactured by Seiko PMC Co., Ltd., trade name) per pulp. , DA4104) 0.15%, alkyl ketene dimer (trade name, Size Pine K) 0.29%, epoxidized behenamide 0.29%, polyamide polyamine epichlorohydrin (Arakawa Chemical Co., Ltd.) Manufactured, trade name, arafix 100) 0.32% was added followed by 0.12% of antifoam.

In the process of making the pulp slurry prepared as described above with a long paper machine and pressing the felt surface of the web against the drum dryer cylinder through the dryer canvas, the tensile force of the dryer canvas is 1.6 kg / After setting to cm and drying, a size press applies 1 g / m ² of polyvinyl alcohol (trade name, KL-118, manufactured by Kuraray Co., Ltd.) on both sides of the base paper, and performs calendar treatment. It was. The base paper was made with a basis weight of 157 g / m ² to obtain a base paper (base paper) having a thickness of 160 μm.

After performing corona discharge treatment on the wire surface (back surface) side of the obtained base paper, MFR (melt flow rate; hereinafter the same) 16.0 g / 10 min, density 0.96 g / cm using a melt extruder. ³ high density polyethylene (hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) 250 ppm and secondary antioxidant (tris (2,4-di-t-butylphenyl) phosphite, Trade name: Irgafos 168, manufactured by Ciba Specialty Chemicals Co., Ltd., containing 200 ppm), MFR 4.0 g / 10 min, low density polyethylene having a density of 0.93 g / cm ³ , 75/25 (mass ratio) ) Was coated so as to have a thickness of 21 g / m ² to form a thermoplastic resin layer having a mat surface (hereinafter, this thermoplastic resin layer). The surface is referred to as “rear surface.”) The thermoplastic resin layer on the rear surface side is further subjected to corona discharge treatment, and then aluminum oxide (trade name, alumina sol 100, manufactured by Nissan Chemical Industries, Ltd.) as an antistatic agent. And a dispersion obtained by dispersing water and silicon dioxide (manufactured by Nissan Chemical Industries, Ltd., trade name, Snowtex O) in water at a mass ratio of 1: 2 so that the dry mass is 0.2 g / m ^2. Subsequently, MFR 4.0 g / 10 min having a corona treatment on the surface and containing 10% by mass of titanium oxide, and a low density polyethylene having a density of 0.93 g / m ² were used with a melt extruder so as to be 27 g / m ^2. A thermoplastic resin layer having a mirror surface was formed.

(Preparation of emulsion A)
Emulsion A was prepared by the following procedure. Compound EB-9 was dissolved in 42 g of a high boiling point solvent (Solv-5) and a high boiling point of 42 g and 20 ml of ethyl acetate, and this liquid was dissolved in 250 g of a 20% by weight gelatin aqueous solution containing 1 g of sodium dodecylbenzenesulfonate (dissolver). ), And 380 g of Emulsion A was prepared by adding water.
Here, the amount of Compound EB-9 added was adjusted to 30 mmol in Emulsion A. However, in the actual experiment, the production scale was changed according to the required amount. At this time, the ratio of each additive and each solvent was set to be the same as described above.
(The structural formula is shown below for reference)

(Preparation of emulsion B)
Emulsion B was prepared by the following procedure. High boiling point solvent (Solv-5) 11.0 g, KF-96 (dimethyl silicone manufactured by Shin-Etsu Chemical Co., Ltd.) 9 g, (EB-9) 15.5 g, (KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)) ) Dissolve in 7.5 g and 20 ml of ethyl acetate, and emulsify and disperse this liquid in 250 g of a 20% by weight gelatin aqueous solution containing 1 g of sodium dodecylbenzenesulfonate with a high-speed stirring emulsifier (dissolver). The emulsion B was adjusted. However, in the actual experiment, the production scale was changed according to the required amount. At this time, the ratio of each additive and each solvent was set to be the same as described above.

(Preparation of thermal transfer image receiving sheets 101-107)
On the support prepared as described above, thermal transfer image-receiving sheets 101 to 107 having a constitution of an undercoat layer 1, an undercoat layer 2, a heat insulating layer, and a receiving layer were prepared in order from the lower layer. The composition and coating amount of the coating solution are shown below.
The coating was performed by the slide coating described above, and the undercoat layer 1 was applied and dried, and then the undercoat layer 2, the heat insulating layer, and the receiving layer were formed by simultaneous multilayer coating. After application, after passing through a set zone of 6 ° C. for 30 seconds to eliminate the fluidity of the liquid, the dry zones are divided into AC as shown in Table 1 below, and the dry bulb temperatures shown in Table 1 in each dry zone (D.B.) and dry air set to relative humidity (RH) are sprayed on the coating surface, and in drying zone A, 0 to 30% of the total moisture content is dried, and in drying zone B, 30 to 60 percent of the total moisture content is dried. The drying zone C was theoretically dried under the condition that 60 to 100% of the total water content was dried (actually, several percent of water remained in the thermal transfer image-receiving sheet even after drying. Is not possible). The kd value in Table 1 below is the amount of water actually evaporated per minute (g / m ² ) / [dry bulb temperature (DB) −wet bulb temperature (WB)). A larger value means faster drying.

Undercoat layer 1 coating liquid (composition)
An aqueous solution obtained by adding 1% sodium dodecylbenzenesulfonate to a 3% gelatin aqueous solution.
Adjust pH to 8 with NaOH (application amount) 11 ml / m ²

Undercoat layer 2 coating liquid (composition)
60 parts by mass of styrene butadiene latex (SR103, trade name, manufactured by Nippon A & L Co., Ltd.)
Polyvinyl alcohol (PVA) 6% aqueous solution 40 parts by mass Surfactant 1% aqueous solution (BFS-1) 2 parts by mass Adjust pH to 8 with NaOH (coating amount) 11 ml / m ²

Heat insulation layer coating liquid (composition)
Emulsion A prepared previously 21 parts by mass Hollow polymer 48 parts by mass (MH5055, trade name, manufactured by Nippon Zeon Co., Ltd.)
10% aqueous gelatin solution 28 parts by weight Water 3 parts by weight Preservative (compound represented by formula PR-1) 0.2 parts by weight Adjust pH to 8 with NaOH (amount of application) 50 ml / m ²

Receiving layer coating liquid (composition)
Emulsion B prepared earlier 4 parts by weight Vinyl chloride polymer latex 53 parts by weight (Viniblanc 900, trade name, manufactured by Nissin Chemical Co., Ltd.)
10 parts by weight of vinyl chloride polymer latex (Vinibrand 276, trade name, manufactured by Nissin Chemical Co., Ltd.)
Microcrystalline wax 6 parts by mass (EMUSTAR-42X, trade name, manufactured by Nippon Wax Co., Ltd.)
Water 22 parts by weight Surfactant 1% aqueous solution (BFS-1) 4 parts by weight Matting agent 1 part by weight (Melamine-silica resin specific gravity 1.65 (Opto beads 3500M, trade name, manufactured by Nissan Chemical Industries, Ltd.))
Preservative (compound represented by formula PR-1) 0.1 part by mass Adjusting pH to 8 with NaOH (application amount) 18 ml / m ²

(Preparation of thermal transfer image-receiving sheet 108 (comparative example))
The said receiving layer coating liquid and the heat insulation layer coating liquid were sequentially apply | coated in order of the heat insulation layer and the receiving layer on the support body. For sequential coating, firstly, a heat insulating layer coating solution is applied onto the support, and after application, the fluidity of the solution is lost by passing through a set zone of 6 ° C. for 30 seconds, and then each of the drying zones A to C is set. It kept in the environment of 25 degreeC50% (DB25.1 degreeC, WB18.1 degreeC), the air blower was stopped, and it dried. Table 1 shows the film surface temperature and the time until 60% of the total water content is dried.

The moisture content is measured from a thermal transfer image-receiving sheet cut out from each of the drying zones A to C, and a 1 cm × 1 cm square is evenly punched in 5 vertical and horizontal locations, and the moisture content (volatile content) is measured by an absolutely dry method. Was obtained from the measured average value.
The film surface temperature was measured using a radiation thermometer “IT-340” manufactured by Horiba.

(Preparation of thermal transfer image-receiving sheet 109 (comparative example))
The said receiving layer coating liquid and the heat insulation layer coating liquid were sequentially apply | coated in order of the heat insulation layer and the receiving layer on the support body. For sequential coating, first, the heat insulating layer coating solution was applied onto the support, and after application, the solution was allowed to pass through a set zone at 6 ° C. for 30 seconds to eliminate the fluidity of the solution, followed by natural drying. Subsequently, the receiving layer coating solution was applied onto the heat insulating layer, and after application, the solution was passed through a set zone at 6 ° C. for 30 seconds to eliminate the fluidity of the solution, and then the thermal transfer image-receiving sheet 101 in Table 1 below was dried. Drying was performed under the same conditions.

(Image formation)
The ink sheet and the heat-sensitive transfer image-receiving sheets 101 to 109 were processed so as to be loaded, and output in a high-speed print mode using a sublimation thermal transfer printer ASK-2000 (manufactured by Fuji Film Co., Ltd.). At this time, the time from the discharge of the first sheet to the discharge of the second sheet was 8 seconds. The output image was a gradation image changing from white to max gray (black solid) or a gradation image changing from white to max magenta (magenta solid).

(Performance evaluation)
About the obtained thermal transfer image receiving sheets 101-109, the performance evaluation test was done on the basis of the following judgment. The results are shown in Table 2.

The evaluation of white spots was performed based on the following judgment using a gradation image from white to max magenta. 5: No white spots are observed in the image and there is no practical problem.
4: No white spots are observed in the magenta solid part, and white spots are slightly observed in the low density part, but there is no practical problem.
3: Almost no white spots are observed in the magenta solid part, but some white spots are observed in the low density part, which is a practical problem.
2: Slight white spots are observed in the magenta solid part, and many white spots are observed in the low density part, which is a practical problem.
1: Many white spots are observed in both the low density portion and the magenta solid, which is a practical problem.

Density unevenness was evaluated based on the following judgment using a gradation image from white to max gray. 5: No density unevenness is observed in the image and there is no practical problem.
4: No density unevenness is observed at all in the black solid part, and slight density unevenness is observed in the low density part, but there is no practical problem.
3: Almost no density unevenness is observed in the black solid part, but some density unevenness is observed in the low density part, which is a practical problem.
2: Slight density unevenness is observed in the black solid part and many density unevenness is observed in the low density part, which is a practical problem.
1: A large number of density unevenness is observed in both the low density portion and the black solid, which is a problem in practical use.

The protective layer transfer failure was evaluated using a gradation image from white to max gray (solid black) and based on the following judgment.
5: No protective layer transfer defect is observed in the image, and there is no practical problem.
4: There is a slight transfer defect of the protective layer in the image, but there is no practical problem.
3: In the image, there is a slight transfer defect of the protective layer on the entire surface, which is a practical problem.
2: In the image, there is a slight protective layer transfer failure on the entire surface, and there is a clear protective layer transfer failure in part, which is a problem in practical use.
1: There is a clear transfer defect of the protective layer on the entire surface of the image, which is a practical problem.

The sensitivity was evaluated using a gradation image from white to max magenta (magenta solid). The visual black density was measured with a Photographic Densitometer (manufactured by X-Rite Incorporated), the density at the point of the black density 1.0 of the thermal transfer image receiving sheet 103 (comparative example) was set to 100, and the relative sensitivity was described by the following judgment. .
5: greater than 116% 4: greater than 108% to 116% or less 3: greater than 100% to 108% or less 2: greater than 92% to 100% or less 1: greater than 86% to 92% or less

Example 2
(Preparation of thermal transfer image-receiving sheets 201-207)
The following heat insulating layer, receptor layer lower layer, receptor layer upper layer coating solution were prepared on the same support as that used for the production of the thermal transfer image receiving sheet 101. The undercoat layer 1 and the undercoat layer 2 were the same as those of the thermal transfer image receiving sheet 101. These coating solutions were applied simultaneously by using a slide coater so that the primer layer 2, the heat insulating layer, the receiving layer lower layer, and the receiving layer upper layer were arranged in this order from the side closer to the support. The coating amount of the undercoat layer 1 and the undercoat layer 2 was the same as that of the thermal transfer image receiving sheet 101.

Heat insulation layer coating liquid (composition)
Hollow polymer particle latex 58.0 parts by mass (MH5055, trade name, manufactured by Nippon Zeon Co., Ltd.)
Gelatin (10% aqueous solution) 30.0 parts by mass (coating amount) 50 ml / m ²
Receiving layer lower layer coating liquid (composition)
12.0 parts by mass of vinyl chloride latex (Viniblanc 690, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
12.0 parts by mass of vinyl chloride latex (Vinibrand 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Gelatin (10% aqueous solution) 10.0 parts by mass The following surfactant F-1 0.1 parts by mass (coating amount) 9 ml / m ²

Receptor layer upper layer coating liquid (composition)
22.0 parts by weight of vinyl chloride latex (Viniblanc 900, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
2.4 parts by mass of vinyl chloride latex (Viniblanc 276, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Gelatin (10% aqueous solution) 2.0 parts by mass The following ester wax EW-1 2.0 parts by mass The following surfactant F-1 0.1 parts by mass The following surfactant F-2 0.4 parts by mass (coating amount) 9ml / m ²

(Image formation)
Similarly to the image formation of the thermal transfer image receiving sheets 101 to 109, the ink sheet and the thermal transfer image receiving sheets 201 to 207 are processed so as to be loaded, and a sublimation thermal transfer printer ASK-2000 (manufactured by Fuji Film Co., Ltd.). And output in high-speed print mode. At this time, the time from the discharge of the first sheet to the discharge of the second sheet was 8 seconds. The output image is a gradation image changing from white to max gray (black solid), or a gradation image changing from white to max magenta (magenta solid), and the same evaluation as that obtained in Table 2 above was performed. went. The results are shown in Table 4 below.

  As is apparent from Table 4, all the samples of the present invention have no white spots caused by cracking due to drying at a high temperature (higher than 20 ° C.), good transfer of the protective layer, and a relatively low viscosity coating during drying. There was no density unevenness due to liquid mixing or aggregation, and the sensitivity was high. According to the present invention, it was found that excellent image formation without image failure can be achieved because of high density printing characteristics and high smoothness.

Claims (4)

  A thermal transfer image-receiving sheet having at least a heat insulating layer and a receiving layer on a support, wherein the receiving layer contains at least one polymer latex, the heat insulating layer contains at least one hollow polymer, and at least two layers A method for producing a thermal transfer image-receiving sheet formed by simultaneous multilayer coating, wherein the production method includes a coating step and a drying step, and at least 60% of the total water content is dried during the drying step. A method for producing a thermal transfer image-receiving sheet, wherein the surface temperature is maintained at 5 ° C. or higher and 20 ° C. or lower.   2. The method for producing a heat-sensitive transfer image-receiving sheet according to claim 1, wherein the time until 60% of the total water content is dried is within 1 minute during the drying step.   The method for producing a thermal transfer image-receiving sheet according to claim 1, wherein the receptor layer and / or the heat insulating layer contains a water-soluble polymer.   4. The method for producing a thermal transfer image-receiving sheet according to claim 3, wherein the water-soluble polymer is polyvinyl alcohol or gelatin.