JP5549170B2 - Protective layer transfer sheet and printed matter - Google Patents

Description

  The present invention relates to a protective layer transfer sheet and a printed matter obtained thereby, and more specifically, in the case where the supply winding of the protective layer transfer sheet is elongated, and the transfer surface of the protective layer transfer sheet after thermal transfer The present invention relates to a protective layer transfer sheet that has good sliding properties with respect to the back surface of the protective layer transfer sheet, and prevents wrinkles, slack, and the like from being caused by winding and thickening.

  Conventionally, a thermal transfer recording method has been widely used as a simple printing method. Since the thermal transfer recording method can easily form various images, the above-mentioned thermal transfer method is represented by computer graphics, still images by satellite communication, CD-ROM, etc. due to the development of various hardware and software related to multimedia. As a full-color hard copy system for analog images such as digital images and videos, the market is expanding. If a full-color gradation image is preferred as a thermal transfer sheet, such as a face photograph, the ink layer is formed on a continuous base film, for example, yellow, magenta, and cyan (and further if necessary) In this case, a large number of color material layers (black) are repeatedly provided in the surface order. Such thermal transfer sheets can be broadly classified as a so-called melt transfer type thermal transfer sheet in which the color material layer is melted and softened by heating, and the color material layer itself is transferred to a transfer target, that is, an image receiving sheet. Thus, the dye in the color material layer is sublimated, and the dye is transferred to the image receiving sheet, and is classified into a so-called sublimation type thermal transfer sheet.

  For example, when creating an ID card such as an identification card using such a thermal transfer sheet, the melt transfer type makes it easy to form line drawings such as letters and numbers, but the durability of the obtained image In particular, there is a drawback that the wear resistance is inferior. On the other hand, the sublimation transfer type is suitable for the formation of gradation images such as facial photographs, but the obtained image is inferior in durability such as abrasion resistance because there is no vehicle unlike ordinary printing ink, Further, when it comes into contact with a card case containing a plasticizer, a file sheet, a plastic eraser, etc., there is a disadvantage that the dye migrates to these, resulting in inferior chemical resistance and solvent resistance such as image blurring. Therefore, as disclosed in Patent Document 1, for the purpose of imparting durability improvement such as abrasion resistance, chemical resistance, and solvent resistance to the formed image, a protective layer transfer sheet serving as a protective layer is formed on the formed image. Attempts have also been made to provide further transfer. For example, by using a protective layer transfer sheet in which a heat-sensitive adhesive layer is provided on a transparent resin layer that is detachably provided on a base film, the heat-sensitive adhesive layer is formed on the image-formed transfer target. And transferring and laminating.

  The protective layer transfer sheet as described above is wound up and rolled to be mounted on a thermal transfer printer for supply. Alternatively, a thermal transfer sheet in which a color material layer such as a dye layer and a thermal transfer protective layer are repeatedly provided in the surface order is wound up, and a roll-like one is mounted for supply to a thermal transfer printer, and thermal transfer recording is performed. In such thermal transfer recording, it is practically required to lengthen the winding for supplying the thermal transfer sheet and reduce the frequency of winding replacement. On the other hand, there is a demand for downsizing the thermal transfer printer and reducing the storage space, and the thermal transfer sheet roll is housed in a limited space. When thermal transfer recording is performed, the thermal transfer sheet roll is mounted on a thermal transfer printer as a supply roll, transferred and used by heating a thermal head, and then wound up as a roll for winding.

  In the above method of use, if the roll to be rolled up has poor sliding properties between the transfer surface after the thermal transfer of the thermal transfer sheet and the back surface of the thermal transfer sheet, wrinkles, slack, etc. occur at the time of winding up, resulting in thickening of the roll. Due to this thickening, there is a problem that the printing roll stops due to contact between the winding roll and a part of the printer body in the printer before the supplied long thermal transfer sheet is used to the end. is there.

JP-A-6-1076

  Therefore, the purpose of the present invention is to provide a longer length of the winding for supplying the protective layer transfer sheet, and the sliding surface between the transfer surface of the protective layer transfer sheet after thermal transfer and the back surface of the protective layer transfer sheet is good, An object of the present invention is to provide a protective layer transfer sheet that prevents wrinkles, slack, and the like from being generated due to wrinkling or slacking when winding.

The above object is achieved by the present invention described below. That is, the present invention provides a protective layer transfer sheet in which a release layer and a protective layer are laminated in this order on at least a part of the opposite surface of a base sheet having a heat resistant slipping layer on one side. The mold layer contains a filler having an average particle size of 1 to 3 μm in a ratio of 0.02 part or more and less than 0.1 part with respect to 100 parts of solid content not including the filler of the release layer, and the thickness of the release layer in the dry state of, wherein Ri 20-80% der having an average particle size of the filler, a resin for forming the heat-resistant lubricating layer of the can, polyvinyl butyral resin, or a polyvinyl acetal resin comprises at least one And

  By taking the above configuration, the protective layer is peeled off from the release layer by heating, and is thermally transferred to the transfer target. In the protective layer transfer sheet after the thermal transfer, the transfer surface of the protective layer transfer sheet and the back surface of the protective layer transfer sheet are excellent in slipping, and wrinkles are generated at the time of winding up to prevent the thickening of the winding. . Furthermore, the surface glossiness of the transferred material to which the protective layer has been transferred is very high, and a printed matter having an excellent appearance can be obtained.

  The filler contained in the release layer is preferably a silicone filler, and can more stably prevent the above-described roll-up. In addition, the release layer coating liquid makes it difficult for the fillers to aggregate, and the production can be stabilized. Moreover, it is preferable that the said protective layer is formed in the surface sequence on the same base material sheet as at least 1 layer of a heat sublimable color material layer or a heat-meltable color material layer. Thus, a protective layer transfer sheet and a thermal transfer sheet provided with a color material layer are not separately prepared, and even in a thermal transfer printer, a protective layer transfer unit in the protective layer transfer sheet and a thermal transfer sheet having a color material layer It is not necessary to install two color material layer transfer units, and only one transfer unit is required, and thermal transfer recording can be performed efficiently.

In the method for forming a printed product of the present invention, a thermal transfer image is obtained by heating a receiving sheet using a thermal transfer sheet in which at least one of a heat sublimable color material layer or a heat meltable color material layer is provided on a base sheet. formed, as subsequently cover the thermal transfer image, the protective layer transfer sheet according to any one of the above, it is to form a printed matter by transferring the protective layer. As a result, prints having various durability can be easily formed.

  According to the protective layer transfer sheet of the present invention, the sliding property between the transfer surface of the protective layer transfer sheet after the thermal transfer and the back surface of the protective layer transfer sheet is good, and wrinkles are generated at the time of winding up, resulting in thickening of the winding. Prevented. Further, the transferred material to which the protective layer has been transferred has the particle size within a certain range as described above, and the specified filler is contained within a certain range with respect to the release layer, and is released. By setting the thickness of the mold layer within a certain range, the surface irregularities of the surface of the release layer and the transferred protective layer were adjusted. As a result, the printed matter to which the protective layer has been transferred can maintain a high surface glossiness and is excellent in appearance.

It is sectional drawing which shows one embodiment which is a protective layer transfer sheet of this invention. It is sectional drawing which shows other embodiment which is a protective layer transfer sheet of this invention. It is sectional drawing which shows one Embodiment of the printed matter obtained with the formation method of the printed matter of this invention.

Next, an embodiment of the invention will be described in detail.
FIG. 1 shows one embodiment which is a protective layer transfer sheet of the present invention. The heat-resistant slip layer 3 is provided on one surface of the base sheet 2, and the protective layer transfer sheet 1 having a structure in which the release layer 4 and the protective layer 5 are laminated in this order on the opposite surface of the base sheet 2. It is. In the protective layer transfer sheet having this configuration, the protective layer and the transfer target are overlapped so that the protective layer 5 is peeled off from the release layer 4 by heating from the heat resistant slipping layer side with a thermal head or the like. Then, it is thermally transferred to the transfer medium. The adhesiveness to the transfer medium can be improved by providing an adhesive layer on the protective layer, without being limited to the illustrated one.

  FIG. 2 shows another embodiment which is a protective layer transfer sheet of the present invention. A heat-resistant slip layer 3 is provided on one surface of the base sheet 2, and a yellow dye layer 61, a magenta dye layer 62, a cyan dye is provided on the other face of the base sheet 2 as a heat sublimation color material layer 6. The layer 63, the heat-meltable black ink layer 7, and the heat-transferable protective layer 5 are repeatedly provided in the surface direction in the flow direction of the base sheet 2. However, a release layer 4 is provided under the heat-meltable black ink layer 7 and the heat-transferable protective layer 5, that is, between the base sheet 2 and the heat-meltable black ink layer 7 and the heat-transferable protection. The peelability at the time of thermal transfer of the layer 5 is improved. A primer layer can be provided between the base sheet and the heat-resistant slip layer, or between the base sheet and the dye layer.

Below, each layer which comprises the protective layer transfer sheet of this invention is demonstrated in detail.
(Substrate sheet)
As the base material sheet 2 constituting the protective layer transfer sheet of the present invention, any material may be used as long as it has a conventionally known degree of heat resistance and strength, for example, 0.5 to 50 μm, preferably 3 to 3 μm. Polyethylene terephthalate film having a thickness of about 10 μm, 1,4-polycyclohexylenedimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, Cellulose derivatives such as cellophane and cellulose acetate, polyethylene film, polyvinyl chloride film, nylon film, polyimide film, ionomer film, etc. In addition, paper such as condenser paper and paraffin paper, nonwoven fabric, or a composite of paper or nonwoven fabric and resin may be used.

(Heat resistant slipping layer)
The protective layer transfer sheet of the present invention has a heat resistant slipping property to prevent adverse effects such as sticking and wrinkles due to the heat of the thermal head on the back surface of the base sheet, that is, the surface opposite to the surface on which the transferable protective layer is provided. Layer 3 is provided. The resin for forming the heat-resistant slipping layer may be any conventionally known resin such as polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene. Resin, styrene-butadiene copolymer, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane or epoxy prepolymer, nitrocellulose resin, cellulose nitrate resin, cellulose acetopropionate resin, cellulose acetate Butyrate resin, cellulose acetate hydrodiene phthalate resin, cellulose acetate resin, aromatic polyamide resin, polyimide resin, polyamideimide resin, polycarbonate Boneto resins, and chlorinated polyolefin resins.

  In addition, in order to improve the heat resistance of the heat resistant slipping layer, the coating film strength and the adhesion to the base sheet, a reaction cured product of a thermoplastic resin having a reactive group in the resin and a polyisocyanate, an unsaturated bond A reaction product with a monomer or an oligomer having a hydrogen atom can be used. The curing method is not particularly limited, and the curing means is not particularly limited by heating or irradiation with ionizing radiation. However, in the protective layer transfer sheet after the thermal transfer of the protective layer, the release layer is exposed on the transfer surface of the protective layer transfer sheet, that is, the surface of the protective layer transfer sheet after the protective layer is transferred. In order to improve the sliding property between the release layer and the back surface of the protective layer transfer sheet (heat resistant slipping layer), in order to reduce the friction coefficient between the release layer containing the filler and the heat resistant slipping layer, The cured type heat-resistant slip layer is preferably used. In particular, a reaction cured product of a thermoplastic resin having a reactive group in the resin and polyisocyanate is preferable because it is practical. Also with the above non-curing resin (thermoplastic resin), a slipperiness-imparting agent and a filler (such as talc) are added to form a heat-resistant slipping layer, and the transfer surface of the protective layer transfer sheet and the protection By improving the slipperiness with the back surface (heat-resistant slipping layer) of the layer transfer sheet, it is possible to prevent wrinkles from occurring due to wrinkles during winding.

  The slipperiness imparting agent added to or overcoated with the heat resistant slipping layer made of these resins includes phosphate ester, silicone oil, graphite powder, silicone graft polymer, fluorine graft polymer, acrylic silicone graft polymer, acrylic siloxane, aryl Examples thereof include silicone polymers such as siloxane, but a layer made of a polyol, for example, a polyalcohol polymer compound, a polyisocyanate compound, and a phosphate ester compound, and a filler is more preferably added.

  The heat resistant slipping layer is prepared by dissolving or dispersing the above-described resin, slipperiness imparting agent, and filler with an appropriate solvent to prepare a heat resistant slipping layer forming ink. It can apply | coat to the back surface of a material sheet | seat by forming means, such as the reverse coating method using a gravure printing method, a screen printing method, and a gravure plate, and can dry and form. The thickness of the heat resistant slipping layer is about 0.1 to 2 μm in terms of solid content.

(Release layer)
The protective layer transfer sheet of the present invention has a structure in which a release layer and a protective layer are laminated in this order on the opposite surface of a base sheet having a heat resistant slipping layer on one side. By providing the release layer 4 between the layers, the release layer during thermal transfer from the base sheet of the protective layer is improved, and the release layer exposed to the surface of the protective layer transfer sheet after the protective layer is transferred However, the slipperiness with the back surface (heat resistant slipping layer) of the protective layer transfer sheet can be improved. The release layer contains a filler having an average particle size of 1 to 3 μm, and the content ratio is 0.02 to 0.4 part with respect to 100 parts of solid content not including the filler of the release layer. And the thickness of a mold release layer is 20-80% of the average particle diameter of the said filler in a dry state.

  When the average particle size of the filler is less than 1 μm, the slipperiness with the back surface of the protective layer transfer sheet is insufficient, and wrinkles or the like are generated at the time of winding, so that winding thickening tends to occur. On the other hand, when the average particle size of the filler is larger than 3 μm, the glossiness of the surface of the protective layer transferred to the transfer medium is lowered, and the surface irregularities become conspicuous. On the other hand, if the content of the filler in the release layer is too low, the slipperiness with the back surface of the protective layer transfer sheet after transfer of the protective layer is insufficient, wrinkles or the like occur during winding, and the roll is likely to be thickened. On the other hand, when the content of the filler in the release layer is too high, the glossiness of the surface of the protective layer transferred to the transfer medium is lowered. Furthermore, if the thickness of the release layer is out of the above range and the thickness is too small, the peelability at the time of thermal transfer from the base sheet of the protective layer is not sufficient, and the glossiness of the surface of the protective layer is lowered. . On the other hand, if the thickness of the release layer is too large, the added filler will not be exposed from the surface of the release layer formed on the base sheet, and the back side of the protective layer transfer sheet after transfer of the protective layer The slipperiness is insufficient, and wrinkles, slack, etc. occur when winding up, and the winding becomes thick.

  The release layer is mainly composed of a binder resin and a filler. As the binder resin, any conventionally known resin having excellent releasability can be used. For example, waxes, silicone wax, silicone resin, silicone-modified resin, fluorine resin, fluorine-modified resin, polyvinyl alcohol, acrylic resin, Examples include acrylic-styrene resins, heat-crosslinkable epoxy-amino resins, and heat-crosslinkable alkyd-amino resins. These release resins can be used alone or as a mixture.

  The release layer can be appropriately selected from those that transfer to the transfer medium during thermal transfer, those that remain on the base sheet side, or those that cohesively break, but the release layer is non-transferable, and thermal transfer The release layer remains on the base sheet side, and the interface between the release layer and the protective layer becomes the surface of the protective layer after the thermal transfer, surface gloss, transfer stability of the protective layer, etc. Since it is excellent in this point, it is preferably performed.

  The filler contained in the release layer has an average particle size of 1 to 3 μm, and silicone resin particles, fluorine-containing resin particles, and the like can be used. Examples of the silicone resin particles include Tospearl (trade name, manufactured by Momentive Performance Materials Japan GK), and examples thereof include Tospearl 120 and 130. Fluorine-containing resin particles include fluorine resins such as polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride, or tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer. It is comprised from 1 type, such as a polymer, fluororesin copolymers, such as ethylene / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer, fluorine rubber, and fluorine elastomer, or a mixture thereof. For example, Asahi Glass Co., Ltd. product name: Full-on PTFE lubricator (L150J, L170J, L172J, L173J) and the like can be mentioned.

  Further, as a filler contained in the release layer, the average particle diameter is 1 to 3 μm, in the dispersion with the binder resin, does not aggregate, and if the gloss of the surface of the protective layer transferred to the transfer object is high, The following particles can be used. Silicone graft acrylic resin [copolymer of silicone macromonomer (dimethylpolysiloxane) and acrylic acid monomer of methyl (meth) acrylate (for example, trade name: X-22-8084, glass transition point: 40 ° C., white It is also possible to use a non-reactive graft resin obtained from [Powder, manufactured by Shin-Etsu Chemical Co., Ltd.].

  Moreover, it is a silicone rubber particle (silicone rubber hardened | cured material) which has a structure which bridge | crosslinked linear dimethylpolysiloxane, and a shape is a spherical or indefinite shape particle | grain. Specifically, trade names: KMP597, KMP598, KMP594, KMP595 (manufactured by Shin-Etsu Chemical Co., Ltd.), trade names: Trefil E-500, E501, E600, E601, E603, E730S (Toray Dow Corning Silicone ( And silicone rubber particles such as those manufactured by the same company). Furthermore, what coated the surface of the spherical silicone rubber particle with silicone resin is also mentioned. For example, trade names manufactured by Shin-Etsu Chemical Co., Ltd .: silicone composite particles (KMP600, X-52-1139G, X-52-1139K), Trefill R-900, R901, R902, R925, R930 (Toray Dow Corning Silicone Co., Ltd.). These particles are silicone composite particles, and the surface of the spherical silicone rubber particles is further coated with a silicone resin.

  The forming method of the release layer can be performed by a known means such as gravure coating, gravure reverse coating, roll coating, etc., using the above-mentioned binder resin, a coating liquid in which a filler is dissolved or dispersed in a solvent, As defined above, the thickness is formed by coating so that it is in the range of 20 to 80% of the average particle diameter of the filler in a dry state.

(Protective layer)
As the resin for forming the protective layer 5, any conventionally known resins having various durability and transparency can be used. For example, an acrylic resin, a cellulose resin, a polyvinyl acetal resin, a polyester resin, etc. are mentioned. In order to form the transferable protective layer from the resin as described above, the resin as described above is added to a general-purpose solvent such as methyl ethyl ketone, toluene, isopropyl alcohol, or the like at an appropriate ratio as described later, for example, a solid content of about 5 to 50 mass%. The coating solution is prepared by dissolving and dispersing so that the thickness (dry basis) of about 0.5 to 5 μm is applied to the surface of the release layer by a conventionally known method such as gravure coating or gravure reverse coating. It is formed by coating and drying.

(Adhesive layer)
In the present invention, when the protective layer has sufficient adhesiveness, it is not necessary to form an adhesive layer, but a heat-sensitive adhesive layer is formed on the surface of the transferable protective layer, Transfer and adhesion of the protective layer after transfer to the image surface can be improved. Any known heat-sensitive adhesive can be used for the adhesive layer, but it is more preferably formed from a thermoplastic resin having a glass transition temperature of 50 to 100 ° C., for example, an ultraviolet-absorbing resin, an acrylic resin, or a chloride. Select a resin with an appropriate glass transition temperature from resins with good thermal adhesive properties such as vinyl-vinyl acetate copolymer resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, polyamide resin, vinyl chloride resin, etc. It is preferable to do. The adhesive layer is prepared by dissolving or dispersing the above-mentioned heat-sensitive adhesive in a general-purpose solvent to prepare a coating solution, and the thickness of the protective layer is measured by a conventionally known method such as gravure coating or gravure reverse coating (dry basis). It is formed by coating and drying so as to be about 0.2 to 5 μm.

(Thermal sublimation color material layer)
The heat sublimable colorant layer 6 formed on the other surface of the base sheet on which the heat resistant slipping layer is provided is a layer containing a sublimable dye. As the sublimation dye, any dye conventionally used in known thermal transfer sheets can be used in the present invention and is not particularly limited. These dyes include methines such as diarylmethane, triarylmethane, thiazole and merocyanine, indoaniline, azomethine such as acetophenone azomethine, pyrazoloazomethine, imidazole azomethine and pyridone azomethine, xanthene and oxazine. Cyanomethylene, thiazine, azine, acridine, benzeneazo, and pyridoneazo, thiophenazo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo represented by dicyanostyrene and tricyanostyrene Azo, such as, disazo, spiropyran, indolinospiropyran, fluoran, rhodamine lactam, naphthoquinone, anthraquinone, quinophthalone It is. Specifically, the following dyes are used.

C. I. (Color Index) Disperse Yellow 51, 3, 54, 79, 60, 23, 7, 141, 201, 231
C. I. Disperse Blue 24, 56, 14, 301, 334, 165, 19, 72, 87, 287, 154, 26, 354
C. I. Disperse thread 135, 146, 59, 1, 73, 60, 167
C. I. Disperse Orange 149
C. I. Disperse violet 4, 13, 26, 36, 56, 31
C. I. Solvent Yellow 56, 14, 16, 29
C. I. Solvent Blue 70, 35, 63, 36, 50, 49, 111, 105, 97, 11
C. I. Solvent Red 135, 81, 18, 25, 19, 23, 24, 143, 146, 182
C. I. Solvent Violet 13
C. I. Solvent Black 3
C. I. Solvent Green 3

  For example, Foron brilliant yellow S-6GL (Sand, Disperse Yellow 231), Macrolex Yellow 6G (Bayer, Disperse Yellow 201) as a yellow dye, and MS-RED-G (Mitsui Toatsu Chemical Co., Ltd.) as a magenta dye Company, Disper Thread 60), Macrolex Red Violet R (manufactured by Bayer, Dispers Violet 26), cyan dye is Kayaset Blue 714 (Nippon Kayaku Co., Ltd., Solvent Blue 63), Foron Brilliant Blue S-R (Sand, Disperse Blue 354), Waxoline Blue AP-FW (ICI, Solvent Blue 36) and the like.

  Next, as a binder resin for carrying the above dye, cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, acetic acid / butyric acid cellulose, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl Examples include vinyl resins such as acetoacetal and polyvinylpyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, and polyester resins. Among these, cellulose , Polyurethane-based, vinyl-based, acrylic-based and polyester-based resins are preferably used in terms of heat resistance, dye transferability and the like.

The heat sublimable colorant layer is prepared by adding these dyes and binder resin to one side of the base sheet, additives (for example, release agents, etc.) and fillers as necessary, and adding toluene, methyl ethyl ketone, Dissolve in a suitable organic solvent such as ethanol, isopropyl alcohol, cyclohexanone, DMF, or disperse in organic solvent or water, and apply by means of gravure printing, screen printing, reverse roll coating printing, etc. It can be worked and dried to form a coating film. The heat sublimable colorant layer thus formed has a coating thickness of 0.2 to 5.0 g / m ^2, preferably about 0.4 to 2.0 g / m ² in a dry state. The sublimable dye in the heat sublimable color material layer should be present in an amount of 5 to 90 mass%, preferably 10 to 70 mass% of the mass of the heat sublimable color material layer. If the image of the desired heat transferable color material layer is monochromatic, select one of the heat sublimable color material layers such as yellow, magenta, cyan, etc., and appropriate if it is a full color image. Each of the sublimation colorant layers of yellow, magenta, and cyan (add black as needed) is selected and formed.

(Hot-melting color material layer)
The heat-meltable color material layer 7 formed on the other surface of the base sheet provided with the heat-resistant slip layer is formed from the following heat-meltable color material layer ink. The heat-meltable colorant layer ink used in the present invention comprises a colorant and a vehicle, and further various additives are added as necessary. As the colorant, among organic or inorganic pigments or dyes, those having a color density required as a recording material and not discolored by light, heat, temperature or the like are preferable. In addition, a substance that develops color when heated or a substance that develops color when brought into contact with a substance applied to the transfer medium can also be used. In addition to cyan, magenta, yellow, black and the like, various colorants can be used as the colorant.

  The vehicle is mainly composed of a wax, and in addition, a mixture of a wax and a drying oil, resin, mineral oil, cellulose, rubber derivatives, or the like is used. In addition, the heat-meltable colored ink layer made of heat-meltable colored ink can contain a heat conductive material in order to give good heat conductivity and melt transferability. Examples of such a heat conductive material include carbonaceous materials such as carbon black, aluminum, copper, tin oxide, and molybdenum disulfide. As a method of forming a heat-meltable color material layer on a substrate sheet using the above-mentioned heat-meltable color material layer ink, hot melt coating, hot lacquer coating, gravure coating, gravure reverse coating, roll coating, etc. A well-known method is mentioned. The thickness of the heat-meltable color material layer comprising the heat-meltable color material layer ink can be appropriately determined in consideration of the required printing density, thermal sensitivity, etc., and is usually about 0.1 to 30 μm. .

(Method for forming printed matter)
In the method for forming a print product of the present invention, the thermal transfer sheet is provided with a thermal transfer color material layer on a base sheet, and the image receiving sheet is heated to form a thermal transfer image, and then cover the thermal transfer image. With the protective layer transfer sheet described in any one of the above, a thermal transferable protective layer is transferred to form a printed matter. That is, first, a thermal transfer image is formed on an image receiving sheet using a thermal transfer sheet provided with a thermal transfer color material layer on a base sheet. At that time, the thermal transfer sheet for forming the thermal transfer image is obtained by sequentially coating the protective layer, the thermal sublimation color material layer, and the thermal transfer color material layer of the heat melting color material layer on the same base sheet. An integrated thermal transfer sheet formed in the above can be used. Further, a thermal transfer sheet provided with a thermal transfer color material layer that is different from the protective layer transfer sheet can be prepared to form a thermal transfer image on the image receiving sheet.

  In the above-described method for forming a printed matter, whether the thermal transfer color material layer and the protective layer are an integral type provided on the same base sheet, or the protective layer alone is provided on the base sheet, either The protective layer transfer sheet is also used as a take-up winding, and after the protective layer is thermally transferred by a heating means such as a thermal head, a pair of rolls (winding) are wound up on the winding for winding. A layer transfer sheet that is mounted on a printer. In the conventional printer, the winding roll of the protective layer transfer sheet becomes larger than planned, and the roll becomes thicker. It was easy for trouble to stop. On the other hand, by using the above protective layer transfer sheet of the present invention, the transfer surface of the protective layer transfer sheet after thermal transfer and the back surface of the protective layer transfer sheet are excellent in slipping, and wrinkles, slack, etc. are generated during winding. It is possible to prevent the occurrence of winding thickening, and the printing is not stopped.

(Printed matter)
FIG. 3 shows an embodiment of a print obtained by the method for forming a print of the present invention. A thermal transfer image-receiving sheet provided with a dye-receiving layer 10 on a substrate 9, and using a thermal transfer sheet provided with a heat-sublimable color material layer or a heat-meltable color material layer on the substrate sheet, the color material layer Then, the color material is transferred to the dye receiving layer 10 to form a thermal transfer image 11. Thereafter, a print 8 having the protective layer 5 transferred thereon is obtained using the protective layer transfer sheet of the present invention so as to cover the thermal transfer image 11 formed on the dye receiving layer 10.

The transfer target to which the thermal transfer image and the protective layer are transferred is not particularly limited. For example, the base material may be any sheet such as plain paper, fine paper, tracing paper, plastic film, etc., and any shape such as card, postcard, passport, letter paper, report paper, notebook, catalog, etc. It is also possible to use a substrate provided with a receiving layer having dye acceptability on the substrate. The receiving layer may be provided by a coating method or thermal transfer using a thermal head or a hot roll. If the substrate itself has dye acceptability, it is not necessary to provide a receptor layer.
The printed matter obtained in the present invention can include character information in addition to image information such as photographs. In this case, for example, character information is formed by a hot-melt transfer method, and image formation such as photographs is performed by sublimation transfer. Can be done in a manner.

Next, the present invention will be described more specifically with reference to examples. Hereinafter, unless otherwise specified, parts or% is based on mass.
(Examples 1-2, Reference Examples 1-4 , Comparative Examples 1-8)
On one surface of the substrate sheet of the easy-adhesion treated polyethylene terephthalate film having a thickness of 6 [mu] m, using a gravure coater at a rate of 1.0 g / m ² of the following heat-resistant lubricating layer 1 coating solution on a solid basis Application and drying were performed to form the heat-resistant slip layer 1. Examples using the base sheet provided with the heat-resistant slip layer 1 are Examples 1-2, Reference Examples 1 , 4 and Comparative Examples 1-7.

<Coating fluid for heat-resistant slip layer 1>
・ 4.55 parts of polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
Polyisocyanate 21.0 parts (Bernock D750-45, solid content 45% by mass, manufactured by Dainippon Ink & Chemicals, Inc.)
・ 3.0 parts of phosphate ester surfactant (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Metal soap (LBT1830, manufactured by Sakai Chemical Industry Co., Ltd.) 0.45 part ・ Talc (Microace P-3, manufactured by Nihon Talc Industry Co., Ltd.) 0.3 part ・ Methyl ethyl ketone 100.0 parts ・ Toluene 100.0 Part

Moreover, in the base material sheet with the heat resistant slipping layer 1, the coating solution for the heat resistant slipping layer 1 is changed to the following coating solution for the heat resistant slipping layer 2, and converted into a solid content using a gravure coater. And dried at a rate of 1.0 g / m ² to form a heat resistant slipping layer 2. Reference Example 2 and Comparative Example 8 use a base material sheet provided with this heat-resistant slip layer 2.
<Coating fluid for heat-resistant slip layer 2>
・ 6.2 parts of polyvinyl butyral resin (ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
・ Metal soap (LBT1830, Sakai Chemical Industry Co., Ltd.) 2.8 parts ・ Talc (Microace P-3, Nippon Talc Industry Co., Ltd.) 1 part ・ Methyl ethyl ketone 25 parts ・ Toluene 25 parts

In the base sheet with the heat resistant slipping layer 1, the coating solution for the heat resistant slipping layer 1 is changed to the following coating solution for the heat resistant slipping layer 3, and converted into solid content using a gravure coater. And dried at a rate of 1.0 g / m ² to form the heat-resistant slip layer 3. Reference Example 3 uses a base sheet provided with the heat-resistant slip layer 3.
<Coating fluid for heat-resistant slip layer 3>
Cellulose acetate butyrate resin 6.2 parts (CAB553-0.4, manufactured by Eastman Chemical Co., Ltd.)
・ Metal soap (LBT1830, Sakai Chemical Industry Co., Ltd.) 2.8 parts ・ Talc (Microace P-3, Nippon Talc Industry Co., Ltd.) 1 part ・ Methyl ethyl ketone 25 parts ・ Toluene 25 parts

On the side opposite to the surface provided with the heat-resistant slip layer of the base sheet, the heat sublimable colorant layer 6 and the heat-meltable black ink layer 7 and the protective layer 5 are the same in the arrangement as shown in FIG. A protective layer transfer sheet formed in the surface order on the base sheet 2 was produced. That is, the yellow dye layer 61 in the arrangement shown in FIG. 2 on the surface opposite to the surface on which the heat-resistant slip layer of the base sheet of polyethylene terephthalate film having a thickness of 6 μm, which has been subjected to the adhesion treatment, is formed. A magenta dye layer 62 and a cyan dye layer 63 were repeatedly formed in this order in the surface order. However, each dye layer of yellow, magenta, and cyan was formed by applying and drying each of the following dye layer coating solutions at a rate of 1.0 g / m ^{2 in} terms of solid content.

<Coating solution for yellow dye layer>
Disperse dye (holon brilliant yellow-S-6GL) 5.5 parts Binder resin 4.5 parts (polyvinyl acetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 0.1 part (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Coating liquid for magenta dye layer>
-Disperse dye (MS Red G) 1.5 parts-Disperse dye (Macrolex Red Violet R) 2.0 parts-Binder resin 4.5 parts (Polyvinylacetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.)
・ Phosphate surfactant 0.1 part (Pricesurf A208N, manufactured by Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

<Cyan dye layer coating solution>
-Disperse dye (Kayaset Blue 714) 4.5 parts-Binder resin (polyvinylacetoacetal resin KS-5, manufactured by Sekisui Chemical Co., Ltd.) 4.5 parts-Phosphate ester surfactant 0.1 parts ( Price Surf A208N (Daiichi Pharmaceutical Co., Ltd.)
・ Polyethylene wax 0.1 part ・ Methyl ethyl ketone 45.0 parts ・ Toluene 45.0 parts

In addition, the following release layer coating solution was applied to the other surface of the substrate sheet (to the easy adhesion treatment surface) and dried to a thickness of 1.0 μm with a gravure coater. The release layer 4 was formed in a pattern with the arrangement shown in FIG.
<Release layer coating solution>
-Silicone modified acrylic resin (Daicel Chemical Industries, Cell Top 226, solid content 50%) 16 parts-Aluminum catalyst (Daicel Chemical Industries, Cell Top CAT-A, solid content 10%) 3 Part / filler described in Table 1 below X part (the X part of the above filler is the addition amount (content ratio) described in Table 1 with respect to 8.3 parts of solid content not including the filler of the release layer) .)
・ Methyl ethyl ketone 8 parts ・ Toluene 8 parts

Further, on the release layer 4, the following heat-meltable black ink layer coating liquid is used, and the heat-meltable black ink layer 7 in the form of a pattern in the arrangement shown in FIG. It was formed by coating and drying to a thickness of 0.0 μm. Further, on the release layer 4, the following protective layer coating solution is applied and dried so as to have a thickness of 1.0 μm in a dry state, and the protective layer is formed into a pattern in the arrangement shown in FIG. 5 were formed, and protective layer transfer sheets of Examples 1-2, Reference Examples 1-4 , and Comparative Examples 1-8 were produced.

<Coating liquid for heat-meltable black ink layer>
・ 20.0 parts of vinyl chloride-vinyl acetate copolymer resin solution (Solvine CNL manufactured by Nissin Chemical Industry Co., Ltd.)
・ Carbon black 10.0 parts ・ Methyl ethyl ketone 35.0 parts ・ Toluene 35.0 parts

<Coating liquid for protective layer>
・ Acrylic resin (Dianar BR87, manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts ・ Methyl ethyl ketone 40 parts ・ Toluene 40 parts

  The protective layer transfer sheets of the above Examples and Comparative Examples were measured and evaluated for the friction coefficient, ribbon diameter increase, and winding thickness. The method is as follows. Furthermore, a printed matter was formed using the protective layer transfer sheet of each example and comparative example, and the glossiness of the printed matter was measured. The method is also shown below.

(Coefficient of friction)
A DPB-6000 printer manufactured by Nidec Copal Corp., using the protective layer transfer sheet of each example and comparative example as the image receiving sheet dedicated to the printer, from each dye layer of yellow, magenta, cyan, yellow, magenta The protective layer transfer sheet after transferring the protective layer of each protective layer transfer sheet so that each dye of cyan is transferred in layers, printed in black, and covered with the black solid image part. prepare. However, the printing environment is normal temperature and normal humidity. The release layer and the heat-resistant slip layer of each prepared protective layer transfer sheet are made to face each other, and a load is applied from above with a weight. (Load is 220 gf)
The dynamic friction coefficient was derived from the dynamic friction force generated when the heat resistant slipping layer side was fixed and the release layer side protective layer transfer sheet was moved. Measuring machines and measurement conditions are as follows.

Measuring machine: Tensilon RTW-500 manufactured by Orientec
Measurement speed: 200 mm / min
Weight: 220g

(Increase ribbon diameter)
A DPB-6000 printer manufactured by Nidec Copal Corp., using the protective layer transfer sheet of each example and comparative example as the image receiving sheet dedicated to the printer, from each dye layer of yellow, magenta, cyan, yellow, magenta Each of the cyan dyes is transferred in a solid gray scale, transferred in gray, solid gray printed, and further, the protective layer of each protective layer transfer sheet is transferred so as to cover the gray solid image portion. However, the protective layer transfer sheet mounted on the printer is a take-up (supply roll) obtained by winding up a long sheet for 600 screens, and the above recording is performed continuously for 600 screens, and the leading end of the supply roll is Used in the form of a pair of rolls wound up on a winding roll. The printing environment is normal temperature and normal humidity. The above gray solid is printed, and one volume of the protective layer transfer sheet is used up (for 600 screens), and the outer diameters of the supply roll before printing and the winding roll after printing are compared. The ratio of the outer diameter of the winding roll after printing to the outer diameter of the supply roll before printing is shown in Table 1. However, the outer diameter was measured with Mitutoyo Digimatic Caliper CD-15CX.

(Rolling over)
The ratio of the outer diameter of the winding roll after printing to the outer diameter of the supply roll before printing measured by increasing the ribbon diameter is 100% to 110%, and the level exceeding 110% is NG level. It is. When the level exceeds 110%, the roll-up roll and a part of the printer body come into contact with each other in the printer before the supplied long thermal transfer sheet is used to the end, and printing stops. This is a trouble.

(Glossiness)
A DPB-6000 printer manufactured by Nidec Copal Corp., using the protective layer transfer sheet of each example and comparative example as the image receiving sheet dedicated to the printer, from each dye layer of yellow, magenta, cyan, yellow, magenta Each dye of cyan is transferred in layers, printed in black, and printed in black, and the protective layer of each protective layer transfer sheet is transferred to cover the black solid image area, and each print is prepared. To do. However, the printing environment is normal temperature and normal humidity. The glossiness of the image surface of each of the obtained prints was measured with the following measuring machine and measurement conditions.
Measuring machine: Gloss Meter VG2000 manufactured by Nippon Denshoku Co., Ltd.
Measurement incident angle: 45 °
Measurement direction: MD: main scanning direction, TD: sub-scanning direction

上記表のフィラー添加量の数値は、離型層のフィラーを含まない固形分１００部に対する、フィラー含有する質量部のパーセンテージを示す。
比較例５におけるフィラーは、表１に示す条件で離型層に添加すると、塗工液の状態で、凝集が生じて、インキの保管安定性が悪く、実用できるものではない。 Table 1 shows the measurement results and evaluation results of the glossiness, friction coefficient, ribbon diameter increase and winding thickness.

The numerical value of the filler addition amount of the said table | surface shows the percentage of the mass part which a filler contains with respect to 100 parts of solid content which does not contain the filler of a release layer.
When the filler in Comparative Example 5 is added to the release layer under the conditions shown in Table 1, aggregation occurs in the state of the coating liquid, and the storage stability of the ink is poor, which is not practical.

From the above table, in Examples 1 and 2 and Reference Examples 1 to 4 , the filler having an average particle size of 1 to 3 μm is 0.025 to 0.3 with respect to 100 parts of solid content not including the filler of the release layer. In the protective layer transfer sheet contained in the ratio of parts, the gloss (TD) is 87% or more, and the gloss (MD) is 90% or more, indicating that the gloss is excellent. Yes. When the glossiness (MD) is 90% or more, it is judged that the surface glossiness is high and the appearance is excellent. When the glossiness (MD) is less than 90%, the surface glossiness is lost.

In Comparative Examples 2, 3, 4, 6, 7, and 8, protective layer transfer containing a filler in a ratio of 0.5 part or 1 part with respect to 100 parts of solid content not including the filler of the release layer The sheets all have a gloss (TD) of less than 85% and a gloss (MD) of less than 88%, indicating poor gloss.
In Comparative Example 1, since the release layer does not contain a filler, the evaluation of the glossiness is good, but the friction coefficient is 0.54, and the protective layer transfer sheet after the protective layer transfer is completed. As a result, the sliding property between the transfer surface and the back surface is insufficient, the winding is loose, wrinkles and the like are likely to occur during winding, and thickening of the winding is likely to occur. In Comparative Example 5, the increase in the ribbon diameter is 107%, which is the limit, and the thickness of the winding is good, but the gloss (MD) is less than 90%, and the surface glossiness is lacking. In addition, from the above results of Examples and Comparative Examples, except for the evaluation of glossiness, if the friction coefficient is suppressed to less than 0.34, the evaluation of the ribbon diameter becomes 107% or less, and the evaluation of winding thickness is also good. It is shown that there is. In Comparative Example 8, the friction coefficient is 0.50, the sliding property between the transfer surface and the back surface of the protective layer transfer sheet after transfer of the protective layer is insufficient, the winding is loose, and wrinkles and the like are generated during winding. It is easy and the result that it is easy to produce overweight.

DESCRIPTION OF SYMBOLS 1 Protective layer transfer sheet 2 Base material sheet 3 Heat resistant slipping layer 4 Release layer 5 Protective layer 6 Heat sublimation color material layer 7 Hot melt black ink layer (heat melt color material layer)
8 Printed matter 9 Base material 10 Dye-receiving layer 11 Thermal transfer image 61 Yellow dye layer 62 Magenta dye layer 63 Cyan dye layer

Claims (4)

In at least a part of the opposite surface of the base sheet having a heat resistant slipping layer on one side, a release layer, a protective layer transfer sheet in which a protective layer is laminated in this order,
The release layer contains a filler having an average particle size of 1 to 3 μm in a ratio of 0.02 part or more and less than 0.1 part with respect to 100 parts of solid content not including the release layer filler,
And the thickness of the release layer is in a dry state, Ri 20-80% der having an average particle size of the filler,
The protective layer transfer sheet, wherein the resin forming the heat resistant slipping layer contains at least one of polyvinyl butyral resin or polyvinyl acetoacetal resin .   The protective layer transfer sheet according to claim 1, wherein the filler contained in the release layer is a silicone filler.   2. The protective layer according to claim 1, wherein at least one of the heat sublimable color material layer or the heat melt color material layer is formed in the same order on the same base sheet. Protective layer transfer sheet. Using a thermal transfer sheet in which at least one of a heat sublimable color material layer or a heat meltable color material layer is provided on a base sheet, a thermal transfer image is formed on the image receiving sheet by heating, and then the thermal transfer image is covered. Thus, the printed matter is formed by transferring the protective layer with the protective layer transfer sheet according to any one of claims 1 to 3 to form a printed matter.

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