JP3410152B2 - Thermal transfer image receiving sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image-receiving sheet, and more specifically, it is capable of forming a recorded image excellent in color density, vividness and various fastnesses, particularly durability such as fingerprint resistance and plasticizer resistance. The purpose is to provide a thermal transfer image-receiving sheet.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer methods are known. Among them, a sublimable dye is used as a recording agent, and a sublimable dye is used as a thermal transfer sheet by supporting it on a base material sheet such as polyester film. Dyeable thermal transfer image receiving sheet,
For example, there has been proposed a method of forming various full-color images on an image receiving sheet having a dye receiving layer formed on paper, plastic film or the like. In this case, the thermal head of the printer is used as the heating means, and a large number of three-color or four-color dots are transferred to the image receiving sheet by heating for an extremely short time, and the full-color image of the original is formed by the multicolor dots. It is to be reproduced. The image formed in this way is extremely clear because the coloring material used is a dye and has excellent transparency, so the resulting image has excellent reproducibility and gradation of intermediate colors, and It is possible to form a high quality image which is similar to the image by offset printing or gravure printing and which is comparable to a full color photographic image.

[0003]

In order to effectively carry out the above-mentioned thermal transfer method, not only the structure of the thermal transfer sheet but also the structure of the thermal transfer image-receiving sheet for forming an image are important. As a conventional technique of the thermal transfer image receiving sheet, for example, JP-A-57-169370 and 57-2 can be used.
07250, 60-25793, 60-648.
99 and 63-82791, etc., vinyl resins such as polyester resins and polyvinyl chloride resins,
A technique for forming a dye receiving layer using a polycarbonate resin, a polyvinyl butyral resin, an acrylic resin, a cellulose resin, an olefin resin, a polystyrene resin, or a dye receiving layer formed by combining these resins with colloidal silica. Techniques for forming are disclosed.

The dye receiving layer of the thermal transfer image-receiving sheet as described above is usually prepared by dissolving the resin as described above in a highly volatile organic solvent such as a general-purpose organic solvent such as toluene, methyl ethyl ketone or ethyl acetate. It is formed by preparing, coating and drying this on the surface of the base material sheet. In this case, since the solvent is volatile, it is easy to dry,
Since the dye-receiving layer-forming resin is essentially lipophilic,
Although the dyeing property of the dye is good and a high density and clear image is formed, when the finger touches the dye image part dyed on the dye receiving layer, the image is affected by the sweat or sebum transferred to the image surface. Discoloration, or the problem that the dye receiving layer itself swells or cracks, that is, the problem of fingerprint resistance, migration of the dye when it comes into contact with a substance containing a plasticizer such as an eraser or a soft vinyl chloride resin product, That is, there are problems of plasticizer resistance and releasability of the thermal transfer sheet during image formation. Therefore, an object of the present invention is to provide a clear image with sufficient density in a thermal transfer method using a sublimable dye,
Moreover, it is an object of the present invention to provide a thermal transfer image-receiving sheet in which an image formed has excellent various fastnesses, particularly excellent fingerprint resistance, plasticizer resistance, releasing property and the like.

[0005]

The above object can be achieved by the present invention described below. That is, the present invention is a thermal transfer image-receiving sheet in which a dye receiving layer is formed on at least one surface of a substrate sheet, wherein the dye receiving layer is formed from a dispersion liquid in which a dye receiving resin is dispersed in an aqueous medium. , The dye receiver
The soluble resin is ethylene glycol as the polyol component.
All polyols including tricyclodecane dimethanol
75 to 90 mol% of the component is the above ethylene glycol
A thermal transfer image-receiving sheet to the polyester resin der wherein Rukoto that.

[0006]

[Function] By forming a dye receiving layer using a dispersion liquid composed of a dye receiving resin which is essentially insoluble in a general-purpose solvent and dispersed in an aqueous medium, fingerprint resistance and plasticity resistance of an image formed are improved. The durability such as the chemical properties is improved. In a preferred embodiment of the present invention, the dye receiving layer is further formed by using an aqueous resin dispersion as described above and a colloidal solution (colloidal silica) of ultrafine particles of water-dispersible or water-soluble silicone oil and / or silicic anhydride. By forming the heat transfer sheet, the releasability of the thermal transfer sheet at the time of image formation is improved. In another preferred embodiment of the present invention, a polyester resin is used as the dye-receptive resin, and the polyester resin comprises
For example, by introducing a small amount of a sulfonic acid group or a group of a salt thereof to impart hydrophilicity that easily disperses in an aqueous medium, a clear image with sufficient density can be obtained without using a general-purpose solvent. It is also possible to provide a thermal transfer image-receiving sheet which has improved durability such as fingerprint resistance and plasticizer resistance of the formed image.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The thermal transfer image-receiving sheet of the present invention comprises a substrate sheet and a dye receiving layer provided on at least one surface thereof. The substrate sheet used in the present invention includes synthetic paper (polyolefin-based, polystyrene-based, etc.),
Fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, etc., cellulose fiber paper, polyolefin, polyvinyl chloride, Films or sheets of various plastics such as polyethylene terephthalate, polystyrene, polymethacrylate and polycarbonate can be used, and a white opaque film formed by adding a white pigment or a filler to these synthetic resins or a foamed sheet formed by foaming. Etc. can be used and are not particularly limited. Further, a laminate in which the above-mentioned substrate sheets are arbitrarily combined can also be used. As an example of a typical laminated body, there is a synthetic paper of cellulose fiber paper and synthetic paper or cellulose fiber paper and plastic film or sheet. The thickness of these base material sheets may be arbitrary, for example, 10 to 30.
Generally, the thickness is about 0 μm. The substrate sheet as described above is preferably subjected to a primer treatment or a corona discharge treatment on the surface when the adhesion with the dye receiving layer formed on the surface is poor.

The dye receiving layer formed on the surface of the substrate sheet is for receiving the sublimable dye transferred from the thermal transfer sheet and maintaining the formed image. In the present invention, as the resin for forming the dye receiving layer,
It is preferable that the main component is a polyester resin that is easily dispersed in an aqueous medium (which may contain an organic solvent).
As a method for making the polyester resin easily dispersible in an aqueous medium, for example, the method described in Japanese Patent Publication No. 61-58092 may be used, but the polyester resin used in the present invention is From the viewpoint of improving the plasticizer resistance, a resin that is insoluble or hardly soluble in a general-purpose organic solvent such as methyl ethyl ketone, toluene, ethyl acetate, chloroform or ethanol is preferable. As a method of making the solvent insoluble or hardly soluble in such a versatile solvent, it is preferable to appropriately select raw materials to be used when synthesizing the polyester. Examples of the acid component of the polyester resin used in the present invention include aromatics such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, and their derivatives. Examples of the group dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and their derivatives. Etc. A particularly preferable acid component is an aromatic acid, and among them, symmetrical aromatic acids such as terephthalic acid and its derivatives are preferable. Furthermore, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, hydroxypivalic acid, γ-butyrilactone, ε-caprolactone, derivatives thereof, and the like can be used in combination as necessary. If necessary, a trifunctional or higher polycarboxylic acid such as trimellitic acid, pyromellitic acid, or a derivative thereof may be used if it is 10 mol% or less based on the total carboxylic acid component.

In the present invention, for the purpose of making the resulting polyester resin insoluble or sparingly soluble in a general-purpose organic solvent and water-dispersible, a part of the aromatic dicarboxylic acid among the above acid components is sulfonic acid or its part. The salt-substituted acid component is preferably used in an amount of 0.5 to 10 mol% of the total acid component, and more preferably 1.0 to 6 mol%. The amount is sometimes water-dispersible dye receptivity resin formed is reduced is less than 0.5 mol%. Preferred aromatic dicarboxylic acids containing these sulfonic acid substitutions (or salt groups thereof) include sulfoterephthalic acid, 5-
Sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid and its lithium, potassium,
Examples include salts of magnesium, calcium, copper, iron and the like. Particularly preferred is 5-sodium sulfoisophthalic acid.

[0010] As the polyol component is another raw material of the polyester used in the present invention, Echirengu recall,
1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol ,, 1,4 cyclohex Nji methanol and tricyclo decanedimethanol (TCD-M), and the like, in order to improve the light fastness of the image formed on the dye receiving layer, it is preferable to use a TCD-M as part of the diol component. If necessary, trifunctional or higher functional polyols such as trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol may be used in combination in an amount of 5% by weight or less based on the total polyol component. In particular, polyethylene glycol having a molecular weight of 106 to 10,000 may be used if necessary in an amount of 5% by weight or less based on the total polyol component. The method for producing the polyester comprising the above components may be a conventionally known method and is not particularly limited. The glass transition temperature of the obtained polyester can be controlled by using terephthalic acid and isophthalic acid. In the present invention, the glass transition temperature is 50
~ 120 ° C is preferable, and the molecular weight is 5,000 ~ 4.
The range of 10,000 is optimal.

Further, in the present invention, it is preferable to use 75 mol% to 100 mol% of ethylene glycol in all polyol components in order to make the obtained polyester resin insoluble or hardly soluble in a general-purpose organic solvent. By using this aqueous dispersion of polyester resin, a thermal transfer image-receiving sheet excellent in fingerprint resistance, plasticizer resistance, etc. can be obtained.
Further, in order to obtain a thermal transfer image-receiving sheet excellent in light resistance,
That use 75 mole% to 90 mole% ethylene glycol out of the total polyol component. In addition, in the present invention, insoluble or hardly soluble means that the solubility of the polyester resin in methyl ethyl ketone, toluene, ethyl acetate, chloroform or ethanol at 25 ° C. is 5% by weight or less. By making it insoluble in this general-purpose solvent, the dye image dyed on the dye receiving layer has good plasticizer resistance and fingerprint resistance. The above example is a preferred method of making the polyester resin used in the present invention insoluble or sparingly soluble in general-purpose organic solvents, but other polyester resins such as a polyethylene oxide group or a carboxyl group are introduced to make the polyester resin hydrophilic. It may be a method of doing.

As a method for dispersing the polyester resin as described above in an aqueous medium, the polyester resin is previously mixed with methanol, ethanol, propanol, butanol,
Echirengu recall, propylene grayed recall, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 3-
Heating in a water-soluble or hydrophilic organic solvent such as methyl-3-methoxybutanol, n-butyl cellosolve acetate, dioxane, ethyl acetate, methyl ethyl ketone, cyclohexanone, cyclooctanone, cyclodecanone, isophorone, particularly preferably butyl cellosolve, ethyl cellosolve, isopropanol. It can be prepared by stirring to obtain a uniform and viscous melt, and then adding the melt to water with stirring at a temperature of 40 to 200 ° C. Water may be added therein.

Further, when the dye receiving layer is formed, the polyester resin dispersion has the glass transition temperature lowered to 50 ° C. or lower, or the glass transition temperature is -20 ° C. or higher, preferably -10 to 10. 90 ° C or less polyvinyl acetate, vinyl acetate / acrylic copolymer, polyacrylic ester, self-crosslinking polyacrylic ester, styrene / acrylic copolymer, polystyrene, ethylene / vinyl acetate copolymer, ethylene / vinyl acetate /
By mixing and using an aqueous dispersion of a resin having a glass transition temperature lower than that of the above polyester resin such as an acrylic terpolymer or polyvinyl chloride, a dye can be obtained without lowering fingerprint resistance and plasticizer resistance. It is possible to improve the dyeing property and the image density. Further, in order to stabilize the dispersed particles of these aqueous dispersions, anionic or nonionic surfactants, polyvinyl alcohol, gelatin, modified polyvinyl alcohol for protective colloid, starch, celluloses and the like may be used. Further, in order to control the glass transition temperature, a low molecular weight or high molecular weight plasticizer may be mixed and used.

The use ratio of the aqueous dispersion of the polyester resin and the aqueous dispersion of the resin having the low glass transition temperature is not particularly limited, but, for example, the former / the latter = on a solid basis.
It is in the range of 0.1 to 10, preferably 1 to 5. Further, in order to improve the light resistance of the image formed, a light stabilizer such as a benzotriazole-based or benzophenone-based UV absorber, an antioxidant such as hindered amine or hindered phenol, and the like are previously added to the dye-receptor. It is preferable that the resin is contained in the layer-forming resin, or these aqueous dispersions are mixed with the resin dispersion before use.

Further, in order to improve the releasability of the thermal transfer sheet at the time of image formation, an aqueous dispersion of the above resin is added.
A water-dispersible or water-soluble modified silicone oil and / or a colloidal solution of ultrafine particles of silicic acid anhydride (colloidal silica), which are commercially available, can be used together in an appropriate ratio. The colloidal solution of ultrafine particles of silicic acid anhydride (colloidal silica) has a particle size of preferably 100 nm or less, and particularly preferably 20 nm or less. Further, the shape of the silica sol is not limited to a spherical shape, and a rod-shaped deformed silica sol colloidal solution having a thickness of 5 to 20 nm and a length of 40 to 300 nm may be used.

Further, in the present invention, in addition to the above polyester resin, a resin conventionally used for forming a dye receiving layer, such as a polyolefin resin such as polypropylene, Halogenated polymers such as vinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl acetate, polyacrylic ester and polyvinyl acetal, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, ethylene and propylene. It is also possible to jointly use a copolymer resin of olefin and other vinyl monomer, an ionomer, a cellulose resin such as cellulose diacetate, a polycarbonate and the like.

The thermal transfer image-receiving sheet of the present invention comprises, on at least one surface of the above-mentioned base sheet, an aqueous dispersion (or a mixture of other resins with an aqueous dispersion) containing a polyester resin as a main component as described above, and Other necessary additives such as release agents, ultrafine inorganic fillers, crosslinking agents, curing agents, catalysts,
A coating solution obtained by adding a thermal release agent and the like to an aqueous dispersion by the method as described above is formed by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate. It is obtained by coating and drying to form a dye receiving layer.

The polyester used as a preferred embodiment of the present invention may have a polymer main chain having a terminal hydroxyl group or a carboxyl group. or,
With respect to the reactive functional groups at these terminals, or the reactive functional groups located on the side chains, for the purpose of improving the coating strength of the dye receiving layer, as long as the object of the present invention is not impaired, epoxy resin, polyisocyanate or It is also possible to cure with a chelating agent such as aluminum, zinc, titanium or zirconium, a cross-linking agent having an aziridine group or an oxazoline group, or a cross-linking agent such as melamine. Further, when a crosslinking agent is used, a known catalyst can be used for each reaction system. When the reactive functional group contained in the polymer chain is a hydroxyl group, for example, Organix TC-300, Organix TC-310, Organix ZB-11 which are chelating agents manufactured by Matsumoto Trading Co., Ltd.
No. 0, Organix AL-135 and the like can be used, and the coating strength of the dye receiving layer can be improved. Further, when the reactive functional group contained in the polymer chain is a carboxyl group, for example, when it is an aziridine crosslinking agent manufactured by Nippon Shokubai, Chemitite PZ-33 and Chemitite DZ are used.
-22E, or Epocros K-1010E, which is an aqueous dispersion of an oxazoline crosslinking agent, Epocros K-1020E,
Epocros K-1030E, Epocros CX-K201
0E, EPOCROS CX-K2020E, EPOCROS CX
-K2030E or CX-WS-140, which is a water-soluble polymer crosslinking agent containing an oxazoline group, can be used, and the coating strength of the dye receiving layer can be improved.

In forming the dye receiving layer, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica, etc. are used for the purpose of improving the whiteness of the dye receiving layer and further improving the sharpness of the transferred image. Pigments and fillers can be added. The dye receiving layer formed as described above may have any thickness, but it is generally 1 to 50 μm thick. Further, such a dye receiving layer may be formed by coating the dispersion liquid at a relatively high temperature to form a continuous coating, or by drying at a low temperature to form a discontinuous coating.

In the dye receiving layer formed as described above, a releasing layer can be formed with an arbitrary releasing agent in order to improve the releasing property from the dye layer of the thermal transfer sheet during printing. However, a preferable release layer is hydroxy-modified, amino-modified,
A reactive silicone such as carboxy-modified or mercapto-modified may be used, and the reactive silicone may be cross-linked with a polyol, a polyisocyanate, an aziridine cross-linking agent, an oxazoline cross-linking agent, or melanmine, if necessary.
When a reactive silicone is crosslinked with a crosslinking agent, a known catalyst may be used depending on the reaction system.
Further, even if the release agent is not formed on the surface of the dye receiving layer, the release effect described above can be obtained by including the release agent in the dye receiving layer. For example, in the polyester aqueous dispersion used as a preferred embodiment of the present invention, a carboxy-modified polydimethylsiloxane X51-789 manufactured by Shin-Etsu Chemical Co., Ltd. is used as a mold release agent to provide mold release property to the dye receiving layer itself. Can be given.

In the case of this example, in order to cure the release agent as necessary, as a crosslinking agent which reacts with a carboxyl group, for example, Organix TC-300, a chelating agent manufactured by Matsumoto Kosho Co., Ltd. Chicks TC-3
10, Organix ZB-110, Organix A
L-135 Chemitite PZ-33 or a Nippon Shokubai made aziridine crosslinking agent, a Chemitite DZ-22E, or aqueous dispersions of <br/> Oki Sa gelsolin based crosslinking agent Epocross K-
1010E, Epocros K-1020E, Epocros K
-1030E, Epocros CX-K2010E, Epocros CX-K2020E, Epocros CX-K2030
E, or CX-CW-140, which is a water-soluble oxazoline group-containing polymer crosslinking agent, can also be used.

When the release agent is cured using a crosslinking agent,
The releasability of the image-receiving sheet for thermal transfer from the thermal transfer sheet can be improved as compared with the case of being uncured. When the polymer that mainly forms the dye receiving layer has reactivity with the cross-linking agent of the release agent, the cross-linking agent is used as the release agent and the dye receiving layer.
A cross-linking reaction occurs with both of the soluble resins. in this case,
The release agent is more firmly fixed to the dye receiving layer as compared with the case where the dye receiving resin does not participate in crosslinking. Further, the image-receiving sheet of the present invention can be applied to various applications such as a sheet or a roll-shaped image-receiving sheet capable of thermal transfer recording, cards, and a transmission type original preparation sheet by appropriately selecting a substrate sheet. I can. Further, the image-receiving sheet of the present invention can be provided with a cushion layer between the base sheet and the dye-receiving layer, if necessary. By providing such a cushion layer, there is little noise during printing and image information can be dealt with. The recorded image can be transferred and recorded with good reproducibility.

The thermal transfer sheet used when performing thermal transfer using the thermal transfer image-receiving sheet of the present invention as described above is a sheet in which a dye layer containing a sublimable dye is provided on a paper or a polyester film, and is conventionally known. Any thermal transfer sheet can be used as it is in the present invention. Further, as the means for applying the thermal energy at the time of thermal transfer, any conventionally known applying means can be used, for example, a thermal printer (for example,
By controlling the recording time with a recording device such as a video printer VY-100 manufactured by Hitachi, Ltd., it is possible to sufficiently achieve the intended purpose by applying thermal energy of about 5 to 100 mJ / mm ^2. I can.

[0024]

EXAMPLES The present invention will be described more specifically with reference to Examples and Reference Examples. In the text, parts and% are based on weight unless otherwise specified. Reference Example 1 In an autoclave equipped with a thermometer and a stirrer, 48 mol of dimethyl terephthalic acid, 4 mol of dimethyl sodium sulfoisophthalate, 48 mol of dimethylisophthalic acid, TC
D-M (20 moles), ethylene glycol (80 moles) and tetrabutyoxy titanate (0.5 moles) as a catalyst were charged and heated at 150 ° C to 220 ° C for 3 hours for transesterification, and then the reaction system was heated to 250 ° C in 30 minutes. Warm up and gradually reduce the system pressure, and after 45 minutes 0.3mmH
The reaction was continued under these conditions for 90 minutes to obtain a light yellow transparent polyester resin 1 (molecular weight 18,000).
0). Similarly, the polyester resins shown in Tables 1 and 2 below were obtained. Furthermore, these polyester resins are melted in butyl cellosolve, and the resulting melt is dropped into water,
A polyester resin dispersion was prepared, and the solid content was adjusted to 30%.

[0025]

[Table 1]

[0026]

[Table 2]

Various performances of the thermal transfer image receiving sheet in the following examples were evaluated according to the following evaluation criteria. Production of thermal transfer sheet used for evaluation A dye-carrying layer-forming ink composition having the following composition was prepared, and a 6 μm-thick polyethylene terephthalate film having a back surface subjected to heat treatment had a dry coating amount of 1.0 g / m ² . In this way, a thermal transfer sheet was obtained by coating with a wire bar and drying. Ink composition; Dye having the following structure 1.0 part Polyvinyl butyral resin 10.0 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 90.0 parts

[Chemical 1]

Evaluation Method The above-mentioned thermal transfer sheet and the thermal transfer image-receiving sheets of Examples and Comparative Examples described later are superposed with their dye layers and dye-receiving surfaces facing each other, and the head applied voltage of 12. 0 V, pulse width 16 msec. Recording was performed with a thermal head under the condition of a dot density of 6 dots / line, and the evaluation method of each performance was performed as follows. (1) Printing Sensitivity (OD) The reflection density of each image was measured with a Macbeth densitometer RD-914, and Comparative Example 1 was set to 1.00 and shown as a relative value. (2) Light resistance test method The printed matter was printed with a xenon fade odometer (Ci-35A, manufactured by Atlas Co.) at 100 KJ / m ² (420n).
m) Irradiation, the change in optical density before and after irradiation was measured by an optical densitometer (RD-918, manufactured by Macbeth Co.), and the residual ratio of optical density was calculated by the following formula. Residual rate (%) = {[optical density after irradiation] / [optical density before irradiation]} × 100 ○; residual rate is 85% or more Δ; residual rate is 80% or more and less than 85% ×; residual rate is 80 %Less than

(3) Fingerprint resistance evaluation method A fingerprint was imprinted on the surface of the printed matter and left at room temperature for 5 days.
The degree of discoloration and density change of the fingerprint imprinted portion was visually evaluated. A: Almost no difference was observed between the fingerprint imprinted part and the non-imprinted part. B: Discoloration or change in density was observed. C: The fingerprint imprinted portion was blank, and the fingerprint shape was clearly recognized. D: White spots occurred around the fingerprint imprinted portion, and at the same time, dye aggregation was observed. (4) Evaluation method of plasticizer resistance The same portion of the printed material surface was lightly rubbed with a commercially available plastic eraser 5 times, and the degree of change in density was visually determined. ◯: Almost no change in density was observed. Δ: A change in density was recognized. Poor: The density changed greatly, and white spots were seen from the low density area to the medium density area.

(5) Releasability Evaluation Method The above thermal transfer image-receiving sheet was applied to a thermal printer (VY-P).
(1 manufactured by Hitachi, Ltd.) was used to continuously perform solid black printing, and the presence or absence of abnormal transfer was visually evaluated. ◯: Black solid printing was continuously performed 5 times or more. B: Black solid printing was performed 1 to 4 times. X: Black solid printing could not be performed even once. The thermal transfer image-receiving sheet of Comparative Example was manufactured as follows.

Comparative Example 1 As a base material sheet, synthetic paper (manufactured by Oji Yuka, thickness 110 μm)
m) and a coating solution having the following composition was applied to one surface of the coating solution with a wire bar at a rate of 5.0 g / m ² when dried and dried to obtain a thermal transfer image-receiving sheet of Comparative Example 1 . The evaluation results were evaluated and the results are shown in Table 2 below. Coating liquid composition; Polyester resin of Comparative Example 1 in Table 1 10.0 parts Catalyst-crosslinking type silicone (X-621212, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 part Platinum catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts of methyl ethyl ketone / toluene (weight ratio 1/1) 89.0 parts

Examples 1 to 3 As a base sheet, synthetic paper (manufactured by Oji Yuka, thickness 110 μm)
4. m), and a dispersion of polyester resin of Table 1 having a solid content of 30% on one surface thereof when dried with a wire bar.
The thermal transfer image-receiving sheets of Examples 1 to 3 were coated and dried at a rate of 0 g / m ² and evaluated according to the above evaluation criteria to obtain the results shown in Table 3 below. The evaluation results of the thermal transfer image receiving sheet of Comparative Example 1 are also shown.

[0033]

[Table 3]

Examples 4 to 6 As a base material sheet, synthetic paper (manufactured by Oji Yuka, thickness 110 μm)
m), and a coating solution having the following composition was applied to one surface of the m) by a wire bar at a rate of 5.0 g / m ² when dried and dried to obtain thermal transfer image-receiving sheets of Examples 4 to 6,
Evaluation was made according to the above evaluation criteria, and the results shown in Table 4 below were obtained. Composition of coating liquid: polyester resin of Tables 1 and 2 (solid content 30%) 100 parts Water-dispersible silicone (X-52-550B, solid content 40%, Shin-Etsu Chemical Co., Ltd.) 7.5 parts

[0035]

[Table 4]

Examples 7 to 8 An aqueous dispersion having a solid content of 30% using the polyester resin shown in Table 1 (without adding water-dispersible silicone) was coated on synthetic paper in the same manner as in Example 1. On the surface of the dye receiving layer formed by
0.2 g / when dried with a wire bar
The thermal transfer image-receiving sheets of Examples 7 to 8 were obtained by coating and drying at a ratio of m ² , and evaluated according to the above evaluation criteria.
The results shown in Table 5 below were obtained. The evaluation results in the case of forming a release layer similarly have One in the thermal transfer image-receiving sheet of Comparative Example 1 are also shown. Coating liquid for release layer Carbinol modified silicone (X-22-160AS, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts Xylylene diisocyanate biuret modified product (XA-14, solid content 40%, manufactured by Takeda Pharmaceutical Co., Ltd.) 125 parts Diol of the following formula 50 parts Methyl ethyl ketone 2,125 parts Dibutyltin dilaurate (isocyanate curing catalyst) 0.1 parts

[0037]

[Chemical 2]

[Table 5]

[0038]

[Effects] According to the present invention as described above, by forming a dye receiving layer using a dispersion liquid composed of a dye receiving resin dispersed in an aqueous medium, fingerprint resistance and plasticity resistance of an image formed can be improved. The durability such as the chemical properties is improved. In a preferred embodiment of the present invention, the dye receiving layer is further formed by using an aqueous resin dispersion as described above and a colloidal solution (colloidal silica) of ultrafine particles of water-dispersible or water-soluble silicone oil and / or silicic anhydride. By forming the heat transfer sheet, the releasability of the thermal transfer sheet at the time of image formation is improved. In another preferred embodiment of the present invention, a polyester resin insoluble in a general-purpose solvent is used as the dye-receptive resin, and a small amount of a sulfonic acid group or a salt group thereof is introduced into the polyester resin. By imparting hydrophilicity that disperses easily in an aqueous medium, without using a general-purpose solvent,
It is possible to provide a thermal transfer image-receiving sheet which gives a clear image with sufficient density and has improved durability such as fingerprint resistance and plasticizer resistance of the image formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Yamada 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Inventor Atsushi Hasegawa 1-chome, Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. 1 within Dai Nippon Printing Co., Ltd. (56) Reference JP-A 1-241491 (JP, A) JP-A 2-122992 (JP, A) JP-A 61-3796 (JP, A) JP-A 4-197786 (JP, A) JP 59-158289 (JP, A) JP 1-166991 (JP, A) JP 1-228891 (JP, A) JP 2-223483 (JP, A) JP-A-2-265789 (JP, A) JP-A-62-294596 (JP, A) JP-A-63-82791 (JP, A) JP-A-4-284293 (JP, A) JP-A-5 -58061 (JP, A) JP-A-5-301464 (JP, A) JP-A-2-223486 (J , A) JP flat 5-581 (JP, A) JP flat 5-64978 (JP, A) (58 ) investigated the field (Int.Cl. ^7, DB name) B41M 5/38 - 5/40

Claims (16)

(57) [Claims] 1. A thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a substrate sheet, wherein the dye-receiving layer is formed from a dispersion liquid in which a dye-receiving resin is dispersed in an aqueous medium , The dye receiving resin is a polyol
Ethylene glycol and tricyclodecane dime as ingredients
75 to 90 mol% of all polyol components including tanol
Is a polyester resin which is the above ethylene glycol . 2. The thermal transfer image-receiving sheet according to claim 1, wherein the dye-receptive resin is a resin which is insoluble or hardly soluble in methyl ethyl ketone, toluene, ethyl acetate, chloroform or ethanol. 3. The thermal transfer image-receiving sheet according to claim 1, wherein the dye-receptive resin is a polyester resin having a hydrophilic group. 4. The thermal transfer image-receiving sheet according to claim 3 Most of the polycarboxylic acid component of the polyester resin is a symmetrical aromatic polycarboxylic acids. 5. The thermal transfer image-receiving sheet according to claim 3, wherein the polycarboxylic acid component of the polyester resin has a small amount of sulfonic acid groups or salt groups thereof. 6. The polyester resin has a molecular weight of 5,000.
˜40,000 and a softening point of 40-20
0 ℃ thermal transfer image-receiving sheet according to claim 3-5 in the range of. 7. The thermal transfer image-receiving sheet according to claim 1, wherein the dispersion further contains a water-dispersible or water-soluble silicone oil and / or a water-dispersible or water-soluble ultraviolet absorber. 8. A dispersion, thermal transfer image-receiving sheet according to claim 1 or <br/> 7 further contains ultrafine particles of colloidal solution (colloidal silica) of silicic anhydride. 9. A thermal transfer image-receiving sheet according to claim 1-8 in which the release layer comprising a reactive silicone to the surface of the dye receiving layer is formed. 10. A dye-receiving layer, the thermal transfer image-receiving sheet according to claim 1 to 7 containing a release agent comprising a reactive silicone. 11. The thermal transfer image-receiving sheet according to claim 1, wherein the dispersion further contains a water-dispersible or water-soluble silicone oil and / or a water-dispersible or water-soluble light stabilizer. 12. The dispersion comprises 25 parts by weight of (A) methyl ethyl ketone, toluene, ethyl acetate or ethanol.
A mixture of an aqueous dispersion of a dye-receptive resin having a solubility at 5 ° C of 5% by weight or less, and (B) an aqueous dispersion of a dye-receptive resin having a glass transition temperature of -10 ° C or higher. The thermal transfer image-receiving sheet described above. 13. The dispersion of (A) is an aqueous dispersion of the polyester resin according to claim 4 or 5 , and
The thermal transfer image-receiving sheet according to claim 1 2 comprising a colloidal silica as described in 8. 14. The dye-receptive resin (B) is selected from the group consisting of polyester, polyvinyl chloride, polyvinyl acetate, styrene-acryl copolymer, vinyl chloride-vinyl acetate copolymer or acrylic microgel. at least a kind, and a thermal transfer image-receiving sheet according to claim 1 2 containing colloidal silica according to claim 8 which. 15. mixed dispersion, the thermal transfer image-receiving sheet according to claim 1 2 or 1 3, further containing a water-dispersible or water-soluble silicone oil and / or water-dispersible or water-soluble light stabilizers. 16. A thermal transfer image-receiving sheet according to claim 1 2, the release layer comprising a reactive silicone to the surface of the dye receiving layer is formed.