JP3150725B2 - Receiving layer transfer 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 transfer sheet for a receiving layer, and more particularly, to a transfer sheet having a coarse image even on a coarse transfer material.
The present invention relates to a receptor layer transfer sheet that provides a dye receiving layer capable of forming a high-quality image without defects such as chipping.

[0002]

2. Description of the Related Art Various thermal transfer methods are known in the art. Among them, a sublimable dye is used as a recording agent, and this is carried on a base film such as paper or plastic film to form a thermal transfer sheet. There have been proposed methods of forming various full-color images on a transfer material such as paper or a plastic film provided with a layer. In this case, a thermal head of a printer is used as a heating means, and a large number of three or four color dots are transferred to a transfer material by heating for a very short time, and a full-color image of an original is formed by the multicolor dots. Is to reproduce. The image formed in this way is very clear because the coloring material used is a dye, and is excellent in transparency, so that the obtained image is excellent in the reproducibility and gradation of intermediate colors. It is possible to form a high-quality image which is similar to an image by offset printing or gravure printing, and is comparable to a full-color photographic image.

[0003]

[Problems to be solved by the invention]
The transfer material on which an image can be formed by the above method is limited to a dye-dyeable plastic sheet or a paper provided with a dye-receiving layer in advance, and cannot directly form an image on ordinary plain paper. There's a problem. Of course, it is possible to form an image even on ordinary plain paper if the receiving layer is formed on the surface thereof, but this is generally costly. For example, postcards, memos, stationery, reports It is difficult to apply to a general ready-made transfer receiving material such as paper. As a method for solving such problems, when an image is to be formed on a ready-made transfer receiving material such as plain paper, a method for easily forming a dye receiving layer only on a necessary portion thereof is a receiving layer transfer sheet. Is known (for example, see Japanese Patent Application Laid-Open No. 62-264994).

However, in the case of using the receiving layer transfer sheet as described above, there is little problem in the case of processed paper having a smooth surface, but in the case of plain paper, postcards, and other papers having a coarse surface, fibers are present on the surface. Since the surface is exposed and lacks the smoothness of the surface, the transfer of the receiving layer is not performed uniformly, and irregularities are generated, or paper fibers are exposed on the surface of the receiving layer. As a result, there is a problem that a blank area or a chip occurs in an image formed on the transferred receiving layer, and a high-quality image cannot be obtained. Accordingly, an object of the present invention is to solve the above problems and to provide a receiving layer transfer sheet capable of forming a high-quality and high-density image with no white spots or chips even on rough paper having a non-smooth surface. That is.

[0005]

The above object is achieved by the present invention described below. That is, the present invention provides a dye receiving layer, an intermediate layer, and an adhesive layer on one surface of a base film in the order described in the description, and the intermediate layer is made of at least a partly crosslinked resin. Characteristic , fiber on the surface
It is a transfer layer transfer sheet for transferring the dye receiving layer to the exposed paper .

[0006]

By forming the intermediate layer of the transfer layer receiving sheet at least partially from a crosslinked resin, the fibers and unevenness of the transfer receiving layer can be obtained even when the fibers are transferred to a coarse-grained paper or the like where the fibers are exposed on the surface. It is possible to form a high-quality and high-density image that does not appear on the surface and has no white spots or chips.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail with reference to preferred embodiments. One example of the receiving layer transfer sheet of the present invention is, as schematically shown in FIG. 1, a release layer (not shown) provided on one side of a base film 1 as necessary, a receiving layer 2 and an intermediate layer 3. And an adhesive layer 4. Incidentally, the receiving layer thermal transfer sheet of the present invention is not limited to the example of FIG. 1, and as shown in FIG. A structure in which one or more color dye layers 7, for example, yellow (7Y), magenta (7M), cyan (7C) and, if necessary, black (not shown) dye layers are provided via an adhesive layer 6. Further, the present invention also includes a configuration (not shown) in which the transfer protection layer 8 and the adhesive layer 9 are provided on the transfer protection layer 8 in the same manner. In addition, 5 and 10 are back layers.

As the base film used in the image receiving layer transfer sheet of the present invention, the same base film as used in the conventional thermal transfer sheet can be used as it is, and other materials can be used. There is no particular limitation. Specific examples of the preferred base film include, for example, thin paper such as glassine paper, condenser paper, and paraffin paper, polyester, polypropylene, cellophane, polycarbonate, cellulose acetate, polyethylene, polyvinyl chloride, polystyrene, nylon, polyimide, and polyvinylidene chloride. And a base film in which these are combined with a plastic such as an ionomer or the above-mentioned paper. The thickness of the base film can be appropriately changed depending on the material so that the strength and heat resistance are appropriate, but the thickness is preferably 3 to 100 μm.

Prior to the formation of the receiving layer, a release layer is preferably formed on the surface of the base film. Such a release layer is formed from a release agent such as a water-soluble resin, a hydrophilic resin, a wax, a silicone wax, a silicone resin, a fluorine resin, and an acrylic resin. The formation method may be the same as the formation method of the receptor layer described below, and the thickness of about 0.01 to 5 μm is sufficient. Also, if a matte receiving layer is desired after transfer,
The release film can be formed into a surface mat by incorporating various particles in the release layer or by using a substrate film having a surface treated with a release layer matt. When it has, it is not necessary to form a release layer.

The dye receiving layer formed on the surface of the base film receives the sublimable dye transferred from the thermal transfer sheet after transferring the receiving layer to an arbitrary material to be transferred, and maintains the formed image. It is for. Examples of the resin for forming the dye receiving layer include polyolefin resins such as polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl acetate and polyacrylester, polyethylene terephthalate, and poly (ethylene terephthalate). Polyester resins such as butylene terephthalate, polystyrene resins, polyamide resins, binary or terpolymer resins of monomers such as vinyl chloride, vinyl acetate, ethylene, propylene, etc., and cellulosic resins such as ionomers and cellulose diacetate , Polycarbonate and the like, and particularly preferred are vinyl resins and polyester resins.

Preferred release agents used by mixing with the above resins include silicone oil, phosphate ester surfactants, fluorine surfactants, etc., but silicone oil is preferred. As the silicone oil, a modified silicone oil such as epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkyl-polyether-modified, epoxy / polyether-modified, or polyether-modified is preferred. One or more release agents are used. or,
The amount of the release agent to be added is preferably 0.5 to 30 parts by weight based on 100 parts by weight of the resin for forming the dye receiving layer. If the addition amount is not satisfied, problems such as fusion of the thermal transfer sheet and the dye receiving layer or reduction in printing sensitivity may occur. By adding such a releasing agent to the dye receiving layer, the releasing agent bleeds out on the surface of the receiving layer after transfer to form a releasing layer.

The receptive layer is formed by dissolving a resin obtained by adding necessary additives such as a releasing agent to the above-mentioned resin on one surface of the base film, or dissolving the resin in an appropriate organic solvent. It is formed by applying and drying a dispersion dispersed in water by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate. In forming the dye receiving layer,
Kaolin clay, for the purpose of improving the foil cut of the receiving layer,
Fillers such as calcium carbonate and finely divided silica can be added. The dye-receiving layer formed as described above may have any thickness, but generally has a thickness of 1 to 50 μm.
Further, such a dye receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating using a resin emulsion or a resin dispersion.

In the present invention, an intermediate layer is provided on the surface of the dye receiving layer. The intermediate layer has a function of preventing fibers or the like exposed on the surface of paper or the like as the material to be transferred from being exposed on the surface of the transfer receiving layer. It is intended to prevent deformation and destruction of the receiving layer, and to prevent the release agent added to the receiving layer from migrating to the adhesive layer and lowering the adhesiveness. preferable. Such a coating is modified to have various reactive groups, for example, polyurethane resin, polyester resin, acrylic resin, polyethylene resin,
Butadiene rubber, epoxy resin, vinyl chloride-vinyl acetate copolymer resin, polyamide resin, binary or ternary copolymer resin of monomers such as vinyl chloride, vinyl acetate, ethylene, propylene, ionomer, cellulose diacetate, etc. Cellulosic resin, polycarbonate resin,
Examples thereof include an electron beam curable resin and an ultraviolet curable resin, and particularly preferable are a reactive acrylic resin and a reactive polyester resin.

Examples of the crosslinking agent for crosslinking the above resin include polyaldehyde, polyamine, polymethylolated product, polycarboxylic acid, polyepoxy compound, polyisocyanate and the like, and polyisocyanate crosslinking agent is particularly preferred. The method of cross-linking may be a conventionally known method, and the cross-linking density is such that the cross-linked film to be formed is not too hard, for example, in the case of a hydroxyl functional polyester resin or acrylic resin, about 0.5 to 30 per 100 parts by weight of the resin. It is preferred to use about parts by weight of polyisocyanate. The intermediate layer formed as described above is generally 0.3 to 10 μm
In the case of a composite thermal transfer sheet provided with a dye layer or a transfer protective layer of each color in a plane-sequential manner as shown in FIG. 2, the thickness of the dye layer is usually several μm. If the layer is too thick, it may be stored in the form of a roll or if it is rewound during image formation, problems such as wrinkles may occur due to the difference in thickness, and if it is too thick because it is a hard layer Cracks may occur due to paper breaks. In this case, in order to solve such problems, the total thickness of the dye receiving layer + intermediate layer + adhesive layer is preferably formed as thin as possible. For example, the thickness of the intermediate layer is about 0.3 to 4 μm. The other layers are formed as thin as possible, and the total thickness is 3 ~
Preferably, the thickness is about 20 μm. Even if the overall thickness is reduced in this way, the intermediate layer is a crosslinked and relatively hard film, so that the adverse effects of the fibers exposed on the surface of the paper during transfer of the receiving layer can be suppressed.

In the present invention, an adhesive layer is further provided on the surface of the intermediate layer in order to improve transferability. These adhesive layers are coated and dried with a solution of a resin having good adhesiveness when heated, for example, a polyamide resin, an acrylic resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, and a polyester resin. By doing so, it is preferably formed to a thickness of about 0.5 to 10 μm. In the present invention, it is also preferable to provide fine irregularities on the surface of these adhesive layers to prevent blocking when the transfer sheet is wound up on a roll and stored. The intermediate layer or the adhesive layer may contain a foaming agent or bubbles to impart excellent cushioning properties to the transfer receiving layer, and may further include a white pigment such as titanium oxide or a fluorescent whitening agent to transfer. The receiving layer can be provided with excellent whiteness and hiding power.

Using the receiving layer transfer sheet as described above,
The transfer material to transfer the transfer layer comprising a receiving layer, card,
Postcard, passport, letter paper, report paper, notebook, catalog, etc., rough the surface of the eye, especially plain paper, which is a rough paper, and the like.
The transfer method of the transfer layer is a general printer equipped with a thermal head for thermal transfer, a hot stamper for a transfer foil, a heat roll, etc., and any heating and pressing means capable of heating to a temperature at which the adhesive layer is activated. Good.

[0017]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified. Example 1 A coating solution for a receiving layer having the following composition was applied to a surface of a 25 μm-thick polyester film (trade name “Lumirror”, manufactured by Toray Industries Co., Ltd.) at a rate of 5.0 g / m ² when dried with a bar coater. Then, after temporarily drying with a drier, drying in an oven at 100 ° C. for 30 minutes to form a dye receiving layer, and then coating the following coating solution for an intermediate layer on the receiving layer at a rate of ² g / m ² at the time of drying. Then, the following coating solution for an adhesive layer is similarly applied at a rate of ² g / m ² at the time of drying and dried to form an adhesive layer, and further subjected to a crosslinking treatment at 120 ° C. for 10 minutes. The receiving layer transfer sheet of the invention was obtained. Coating liquid composition for receptor layer ; vinyl chloride / vinyl acetate copolymer (VYHD, manufactured by Union Carbide) 100 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Amino-modified silicone (KS-343, Shin-Etsu 6 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts

The intermediate layer coating liquid composition, acrylic resin (ants Dick A, manufactured by Dainippon Ink and Chemicals) 100 parts of an isocyanate resin (Sumidule N, Sumitomo Bayer) 5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts Coating liquid composition for adhesive layer ; Polymethyl methacrylate resin (BR-106, manufactured by Mitsubishi Rayon) 100 parts Titanium oxide (TCA-888, manufactured by Tochem Products, TCA888, average particle size 0.2 μm) 50 parts Methyl ethyl ketone / Toluene (weight ratio 1/1) 300 parts

Example 2 The receiving layer transfer sheet of the present invention was prepared in the same manner as in Example 1 except that the following coating liquid was used (thickness: 2 g / m ² ) instead of the intermediate layer coating liquid in Example 1. Was formed. Coating liquid composition for intermediate layer ; polyester resin (Vylon 200, manufactured by Toyobo) 100 parts Isocyanate resin (takenate D-102, manufactured by Takeda Pharmaceutical) 10 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts Example 3 The following coating solution was used in place of the coating solution for the intermediate layer in Example 1 (thickness: 2 g / m ² ), dried after coating, and irradiated with an electron beam to form a receiving layer transfer sheet of the present invention. Intermediate layer coating solution composition, acrylic monomers (DPHA, manufactured by Nippon Kayaku Co.) 100 parts of acrylic monomer (Viscoat # 295, Osaka Organic Chemical Co., Ltd.) 30 parts Methyl ethyl ketone / toluene (1/1 by weight) 300 parts Example 4 A receiving layer transfer sheet of the present invention was formed in the same manner as in Example 1 except that the following coating liquid was used instead of the coating liquid for the intermediate layer in Example 1 (thickness: 2 g / m ² ). Coating liquid composition for intermediate layer ; acid-functional polyester resin (Uralax P2200, manufactured by Urachem) 100 parts Modified melamine resin (RF-3403, manufactured by Monstant) 15 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts

Example 5 A coating liquid for a receiving layer having the same composition as in Example 1 was dried on a surface of the same base film as in Example 1 with a bar coater.
0 g / m ² , preliminarily dried with a drier, and dried in an oven at 100 ° C. for 30 minutes to form a dye receiving layer. the layers coating liquid is coated and dried in sequence at the rate of each dry 2 g / m ^2, coating and further at a rate of example 1 and the same adhesive layer coating solution in the same manner dry 2 g / m ² It was dried to form an adhesive layer, and further subjected to a crosslinking treatment at 120 ° C. for 10 minutes to obtain a receptor layer transfer sheet of the present invention. Intermediate layer coating liquid composition: Acrylic polyol resin (thermo rack U230, Soken Kagaku Co., Ltd.) 100 parts Titanium oxide (TCA-888, manufactured by Tochem Products) 50 parts Polyisocyanate resin (Takenate D-102, manufactured by Takeda Chemical Industries ) 10 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts Coating composition for foam layer ; Acrylic emulsion (AE-120, manufactured by Nippon Synthetic Rubber Co., Ltd., Tg = -10 ° C.) 100 parts Thermal foaming microcapsules (F -30D, Matsumoto Yushi Pharmaceutical) 10 parts

Example 6 A receiving layer coating liquid having the same composition as in Example 1 was dried on a surface of the same base film as in Example 1 by a bar coater.
Coating at a rate of 0 g / m ² , preliminary drying with a drier, drying in an oven at 100 ° C. for 30 minutes to form a dye receiving layer, and coating on the receiving layer for the same intermediate layer as in Example 5. The liquid was applied and dried at a rate of ² g / m ² at the time of drying, and the following coating liquid for the foamable adhesive layer was dried in the same manner.
The foamed adhesive layer was formed by coating and drying at a ratio of g / m ² , and further subjected to a crosslinking treatment at 120 ° C. for 10 minutes to obtain a receptor layer transfer sheet of the present invention. Coating composition for foaming adhesive layer ; polymethyl methacrylate resin (BR-106, manufactured by Mitsubishi Rayon Co., Ltd.) 100 parts Thermal foaming microcapsules (F-30D, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) 10 parts Titanium oxide (TCA-888, Tokam Products, TCA888, average particle size 0.2 μm) 50 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts

Comparative Example 1 A receiving layer transfer sheet of Comparative Example was formed in the same manner as in Example 1 except that the thickness of the intermediate layer in Example 1 was changed to 3 g / m ² . Comparative Example 2 A receiving layer transfer sheet of a comparative example was formed in the same manner as in Example 1 except that the intermediate layer was not formed.

On the other hand, an ink for a dye layer having the following composition was prepared, and applied to a 6 μm-thick polyethylene terephthalate film whose back surface was subjected to heat treatment at a dry coating amount of 1.0 g / m ^2.
Apply and dry with a wire bar so that it becomes like this. Further, drop a few drops of silicone oil (X-41 / 4003A, made by Shin-Etsu Silicone) on the back with a dropper, spread it over the entire surface and coat it on the back to obtain a thermal transfer sheet. Was. Ink composition for dye layer : Disperse dye (Kayaset Blue 714, manufactured by Nippon Kayaku) 4.0 parts Ethyl hydroxycellulose (manufactured by Hercules) 5.0 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 80.0 parts Dioxane 10.0 parts The receiving layer transfer sheet and plain paper were overlapped, and the receiving layer was transferred using a hot roll. Next, the thermal transfer sheet is overlaid on the surface of the receiving layer, and printing is performed using a thermal head under the conditions of an output of 1 W / dot, a pulse width of 0.3 to 0.45 msec., And a dot density of 3 dots / mm, and a cyan image. Was formed. Table 1 shows the quality of the cyan image obtained as described above.

[0024]

[Table 1]

Example 7 A heat-resistant lubricating layer was formed on the back surface, and the other surface was subjected to a release treatment. 90c
m, a coating liquid for a receiving layer having the following composition was applied by a bar coater at a rate of 2 μm when dried, and was temporarily dried with a drier, and then dried in an oven at 100 ° C. for 30 minutes to form a dye receiving layer. Further, the intermediate layer and the adhesive layer (total thickness of the receiving layer + intermediate layer + adhesive layer: 8 g /
m ² ). Coating solution composition for receptor layer Vinyl chloride / vinyl acetate copolymer resin (VYHD, manufactured by Union Carbide) 100 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Amino-modified silicone (X-22-343, Shin-Etsu Chemical Co., Ltd. 8 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Coating composition for middle layer ; bisphenol A type epoxy resin (araldide, molecular weight 3,750, Ciba-Geigy) 100 parts Polyamine (ADEKA) Hardener EH-220, Asahi Denka) 5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 300 parts Coating liquid composition for adhesive layer Acrylic resin (BR-106, manufactured by Mitsubishi Rayon) 100 parts Methyl ethyl ketone / toluene (weight ratio) 1/1) 300 copies

Subsequently, a coating liquid for an adhesive layer having the following composition and 3
The coating solution for the dye layer of each color was prepared, and the coating amount for the adhesive layer and the coating solution for the dye layer were dried in the order of 30 cm on the surface of the base film on which the receiving layer was not formed, respectively. Was applied by a gravure coater and dried so as to be 0.5 μm and 1.0 μm, respectively, to obtain a composite thermal transfer sheet of the present invention. Coating solution composition for adhesive layer: polyester resin (Adcoat 335A) 35 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 65 parts Yellow dye layer coating solution composition : disperse dye (Macrolex Yellow 6G, manufactured by Bayer AG) 5.5 parts Polyvinyl butyral resin (S-LEC BX-1, manufactured by Sekisui Chemical) 4.5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 89.0 parts In the same manner, the coating liquid for the magenta dye layer is a disperse dye. (C.
I. Disperse Red 6G) and a coating solution for the cyan dye layer were prepared using a disperse dye (CISolvent blue 63), respectively.

Example 8 In Example 5, a transferable protective layer having a coating weight of 2 g / m ^{2 on} the surface was formed next to the dye layer from a coating liquid for a protective layer having the following composition to form a composite of the present invention. A thermal transfer sheet was obtained. Coating liquid composition for protective layer : polyester resin (Vylon 600, manufactured by Toyobo) 20.0 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical) 0.5 part methyl ethyl ketone / toluene (weight ratio 1/1) 80.0 Part The receiving layer surface of the composite thermal transfer sheet of the present invention is superimposed on a postcard, and using a thermal head, under the conditions of an output of 1 W / dot, a pulse width of 0.3 to 0.45 msec., And a dot density of 3 dots / mm. The receiving layer was transferred over the entire surface, and then a yellow signal obtained by color separation of the original was printed on the surface of the receiving layer, and a yellow dye layer was superposed to form a yellow image. Further, a magenta dye is similarly transferred to the image area obtained above by a magenta signal, and a cyan dye is further transferred by a similar cyan signal to form a full-color image. Further, in the case of Example 6, a protective layer is formed on the image surface. Transcribed. As a result, excellent full-color images were obtained in the same manner as in Examples 1 to 4.

[0028]

According to the present invention as described above, the intermediate layer of the receiving layer transfer sheet is formed from at least a partly crosslinked resin, so that the fibers can be transferred to a coarse paper or the like whose surface is exposed. Fibers and irregularities do not appear on the surface of the transfer receiving layer, and it is possible to form a high-quality and high-density image without white spots or chipping. Further, when a composite thermal transfer sheet is used, the overall thickness of the transferability receiving layer can be reduced.

[0029]

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a cross section of a receiving layer transfer sheet of the present invention.

FIG. 2 is a diagram schematically illustrating a cross section of the receiving layer transfer sheet of the present invention.

[Explanation of symbols]

 1: base film 2: receiving layer 3: intermediate layer 4: adhesive layer 5: back layer 6: adhesive layer 7: dye layer 8: protective layer 9: adhesive layer 10: back layer

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-160682 (JP, A) JP-A-2-261693 (JP, A) JP-A-3-126585 (JP, A) 69672 (JP, U) Actually open 1986-71428 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (3)

(57) [Claims] 1. A dye-receiving layer on one side of a base film,
It is provided an intermediate layer and an adhesive layer on the order of this description, the intermediate layer is characterized in that it consists at least partially crosslinked resin, paper the dye receiving the fibers is exposed on the surface
Receiving layer transfer sheet for transferring the container layer . 2. The receiving layer transfer sheet according to claim 1, wherein the intermediate layer comprises a polyester resin and / or an acrylic resin, and the crosslinking agent is a polyisocyanate. 3. The receiving layer transfer sheet according to claim 1, wherein the dye layer and / or the transfer protective layer are further formed in a plane-sequential manner.