JP3056693B2 - Heat transfer sheet for transparent manuscript creation - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used for an overhead projector (OHP) or a slide projector, or for diazo copy or photolithography. The present invention relates to a heat-transferable sheet for producing a transparent original, which is suitable for producing a printable material, in other words, a transparent original by transferring a color material from a thermal transfer sheet. 2. Description of the Related Art Sheets for creating transparent originals are conventionally
Photographic films such as (a) silver halide photographic films and (b) diazo photographic films are mainly used. But,
In the case of the photographic films (a) and (b), the image formation is performed optically, and the steps of exposure and development, and, if necessary, fixing are required for each material, although slightly different depending on the material. In recent years, there has been an increasing demand for directly creating and using a hard copy from an electric signal such as an image on a CRT. In response to these requirements, a heat transfer sheet provided with a sublimable disperse dye layer having the property of being transferred by heating is used in combination with a heat transfer sheet, and the sublimable disperse dye is transferred onto the heat transfer sheet while controlling. A method for obtaining an image such as a photograph with gradation has been proposed. This method is an application of a method used as a method for dyeing a heat transfer sheet made of polyester fiber using a heat transfer sheet. A thermal head is used as a typical heating means for hard copy, but heating by the thermal head is usually extremely short. As an example, the transfer condition to the polyester fiber is 20
The printing condition of the thermal head is about several milliseconds at 400 ° C., although it is about 1 minute at 0 ° C. For this reason, it has been impossible to transfer to a polyester fiber by using a conventional combination of a thermal transfer sheet and polyester fiber and using a thermal head, and it was also impossible to create a transparent original. Accordingly, an object of the present invention is to provide a heat transfer sheet which can be printed with a thermal head and can be viewed with transmitted light. [0004] The present invention is used in combination with a thermal transfer sheet having a dye layer containing a sublimable dye transferred by heating on one surface of a support and having a slipping layer on the opposite surface of the support. A heat transfer sheet for creating a transparent original, a dye-fixable resin coating having a thickness of 2 to 10 μm, which receives a dye transferred from the heat transfer sheet when heated on a transparent substrate, and Average particle size 10-10
0 mμ and a silica powder having a specific surface area of less than 250 m ² / g
The present invention relates to a heat-transferable sheet for producing a transmission original, wherein a receptor layer containing about 20% by weight is laminated, and a dye-permeable release agent layer is provided on a part of the receptor layer. Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1 , a heat-transfer sheet for producing a transparent original (hereinafter often referred to as a heat-transfer sheet) 1 according to a first embodiment of the present invention, as shown in FIG. A dye-permeable release agent layer 4 is provided on a part of the layer 3. (Substrate) The substrate 2 has a role of holding the receptor layer 3 and has a mechanical strength that does not hinder handling even in a heated state because heat is applied during thermal transfer. Further, it is desirable to have transparency. Specific examples of such a transparent substrate 2 include polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film, and ethylene vinyl acetate. Among plastic films such as polymer films, ethylene vinyl alcohol copolymer films, and ionomers, transparent or translucent ones (which may be colored transparent or colored translucent) can be used. Mechanical devices prevent breakage during handling. When importance is placed on properties and heat resistance, polyethylene terephthalate film, polycarbonate film and nylon film are preferred, and polyethylene terephthalate film is particularly preferred. It has been. The thickness of the substrate 2 is usually 3 to 50 μm, preferably about 5 to 15 μm. (Receiving layer) Receiving layer 3 of thermal transfer sheet 1
As described above, has the function of receiving the dye transferred from the thermal transfer sheet when heated, and specifically, the following is used. (A) Those having an ester bond: polyester resin, polyacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin and the like. (B) Those having a urethane bond, such as polyurethane resins. (C) A polyamide resin having an amide bond. (D) Those having a urea bond, such as urea resins. (E) Other resins having a highly polar bond such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin and polyacrylonitrile resin. In addition to the above synthetic resins, mixtures or copolymers thereof may also be used. The receiving layer 3 may be formed of two kinds of resins having different properties. For example, -100 ~
The first region of the receiving layer is formed of a synthetic resin having a glass transition temperature of 20 ° C. and having a polar group.
The second region of the receiving layer can be formed of a synthetic resin having a glass transition temperature of not less than ° C. The first region and the second region are both exposed on the surface of the receiving layer, and
The regions occupy 15% or more of the surface, and the first regions are present independently of each other in an island shape, and the length of each of the island portions in the longitudinal direction is preferably 0.5 to 200 μm. . The release agent layer 4 is made of a solid wax, a fluorine- or phosphate-based surfactant, a silicone oil, or the like. As the solid wax, polyethylene wax, amide wax, Teflon powder or the like is used. Phosphate surfactants include Plysurf A208S and Plysurf A210
G, Price Surf DB-01 (Daiichi Kogyo Pharmaceutical), Gaffa RS-410, Gaffa RA-600, Gaffa RE-6108 or more Toho Chemical Co., Ltd., and Unidyne DS501 and Unidyne DS502 as fluorine surfactants (Daikin Industries), FC430, FC
431 (Sumitomo 3M) and the like. Oily silicone oils can be used, but curable silicone oils are preferred. Examples of the curable silicone oil include a reaction curable type, a photocurable type, and a catalyst curable type. Of these, reaction-curable silicone oils are particularly preferred. The reaction-curable silicone oil is preferably one obtained by reacting and curing an amino-modified silicone oil and an epoxy-modified silicone oil. Specific examples of amino-modified silicone oils include Shin-Etsu Chemical Co., Ltd.
KF-393, KF-857, KF-858, X-
22-3680, X-22-3801C, etc., while epoxy-modified silicone oils include KF
-100T, KF-101, X-60-164, KF-
103 or the like is used. As a catalyst or a photo-curable silicone oil, KS705F-PS (catalyst), K
S705F-PS-1 (catalyst), KS-720, KS7
70-PL-3 (catalyst), KS774-PL-3 and the like. The release agent layer 4 is formed by dissolving or dispersing the aforementioned release agent in an appropriate solvent, and applying the obtained solution or dispersion on the receiving layer 3. And then dried. The thickness of the release agent layer is 0.01 to 5 μm.
m, preferably 0.05 to 2 μm.
If the thickness of the release agent layer is less than 0.01 μm, a sufficient release effect cannot be obtained, while if it exceeds 5 μm, the dye permeability is undesirably hindered. In general, it is difficult to print an explanatory note or the like on a release agent layer, but it is possible to print on a receptor layer. Therefore, when it is necessary to print on the heat transfer sheet, it is preferable to provide the release agent layer only on a part of the receiving layer. The heat transfer sheet of the first embodiment according to the present invention is characterized in that the above-mentioned receiving layer contains fine silica powder. In the present invention, silica is
Refers to silicon dioxide or a substance containing silicon dioxide as a main component. The finely divided silica to be contained in the receiving layer has an average particle diameter of 10 to 100 mμ and a specific surface area of less than 250 m ² / g, and more preferably has an average particle diameter of 10 to 50 mμ and a specific surface area of 20 to ²⁰⁰ m ² / g. Is used. When the average particle diameter of the finely divided silica is larger than this range, the dispersion stability of the finely divided silica in the coating composition for the heat transfer layer used for forming the receiving layer is reduced, and the smoothness of the surface of the receiving layer of the heat transfer sheet is reduced. This is significantly impaired, and the image obtained by thermal transfer becomes unclear. When the average particle diameter of the finely divided silica is smaller than this range, the fluidity of the coating composition for the heat transfer layer used for forming the receiving layer is reduced, and the effect of adding the fine powder silica to the heat transfer sheet is sufficiently exhibited. Not done. Specific examples of the fine powder silica satisfying such conditions include A
EROSILR972, AEROSIL 130, AE
ROSIL 200, AEROSILOX50, AER
OSIL TT600, AEROSIL MOX80,
AEROSIL MOX170 (Aerosil Co., Ltd. silica fine powder) and the like. The content of the finely divided silica is 5 to 20% by weight, more preferably 5 to 20% by weight, based on the weight of the receiving layer.
It is in the range of 10% by weight. These fine silica powders are previously added to the resin constituting the receiving layer, and the obtained resin mixture solution is applied on a substrate and dried to form a receiving layer. When forming the receiving layer, various additives may be added in addition to the above-mentioned finely divided silica, but those components are selected from those which do not hinder the fixation of the dye migrating from the thermal transfer sheet when heated. It should be. The heat transfer sheet according to the second aspect of the present invention has a receiving layer formed by providing a dispersion coating film comprising at least one resin and water on a substrate and then drying the coating. . As the resin as a dispersoid constituting the dispersion with water, (a) a resin having a single type of dyeing ability, and (b) a resin of the same type and having high and low dyeing ability And (c) a mixture of one or more resins having at least one kind capable of being dyed and having no compatibility with each other. It is considered that the magnitude of the dyeing ability of the resin is substantially proportional to the physical properties of the resin, particularly the glass transition temperature. Generally, the glass transition temperature is -100.
It can be said that resins having a glass transition temperature of 40 ° C. or higher generally have high dyeing ability. In the present invention, the term “dispersion liquid” includes both a liquid-liquid dispersion system (emulsion) and a liquid-solid dispersion system (suspension). Preferred specific examples of the above-mentioned resin-water dispersion include the following. (A) natural rubber latex (concentrate of natural rubber sap) (b) synthetic rubber latex (synthetic rubber aqueous dispersion obtained by emulsion polymerization) SBR (styrene / butadiene copolymer) latex
Polychloroprene latex, polybutadiene latex, butyl rubber (polybutene) latex, etc. (C) Synthetic resin emulsion (synthetic resin aqueous dispersion obtained by emulsion polymerization) Polyacrylate emulsion, polyvinyl acetate emulsion, ethylene / vinyl acetate copolymer emulsion, polystyrene emulsion, polyvinyl chloride emulsion and the like. (D) Synthetic resin aqueous dispersion (synthetic resin aqueous solution obtained by dispersing a synthetic resin solution or a synthetic resin melt in water) Polyester aqueous dispersion, polyurethane aqueous dispersion, polyethylene aqueous dispersion and the like. The aqueous resin dispersion described above may contain a dispersant for stabilizing the dispersion. Preferred specific examples of the dispersant to be added include the following. (1) Emulsifiers Anionic surfactants such as carboxylates, sulfonates, sulfates, phosphates, and phosphonates, amine salts, quaternary ammonium salts, phosphonium salts, and sulfonium salts. Cationic surfactants,
Amphoteric surfactants such as betaine and sulfobetaine; nonionic surfactants such as fatty acid monoglycerin esters and fatty acid polyglycol esters; (2) protective colloid polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyacrylic acid, polymethacrylic acid, hydroxyethyl cellulose, hydroxypropyl cellulose,
Methyl cellulose, ethyl cellulose and the like. (3) Self-emulsifiable resin, such as a polar group-containing polyurethane, in which the dispersing resin itself has polarity and localizes on the particle surface to impart dispersion stability. The composition of the resin aqueous dispersion described above is, by weight,
Resin component 20-70%, more preferably 30-60%,
The water content is in the range of 30 to 80%, more preferably 40 to 70%. The dispersant is added in a weight ratio of 0.1 to 10%, preferably 1 to 5% with respect to the resin component. Various additives may be added to the aqueous resin dispersion, and these components should be selected from those which do not hinder the fixation of the dye migrating from the thermal transfer sheet when heated. . The formation of the receptor layer with the aqueous resin dispersion having the above composition is carried out by first providing an aqueous resin dispersion coating film on a substrate by an appropriate printing method or coating method, for example, a method such as wire bar coating. This is performed by drying. The thickness of the receiving layer can be appropriately selected according to the type of the base material and the like.
m, preferably in the range of 2 to 10 μm. As the composition for forming a release layer on the surface of the receptor layer for improving the releasability from the thermal transfer sheet, a cured product of a silicone compound, for example, a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil And the like are preferably used. Details of each of these modified silicone oils are as described above. (Thermal Transfer Sheet) The heat transfer sheet 1 according to the first to third aspects of the present invention has a dye layer containing a sublimable dye which is transferred by heating on one surface of the support, Is used in combination with a thermal transfer sheet having a lubricating layer on the side opposite to. A typical thermal transfer sheet 5 is
As shown in FIG. 4, a heat transfer layer 7 is provided on one surface of a support 6, and when the heat transfer layer 7 is heated, the coloring material contained therein moves to the heat transfer sheet. It is supposed to. Examples of such coloring materials include disperse dyes having a relatively small molecular weight of about 150 to 400, oil dyes, certain basic dyes, and intermediates which can be changed to these dyes. It is selected and used in consideration of thermal transfer temperature, thermal transfer efficiency, hue, color rendering, weather resistance and the like. The above color material is provided on the support 6 by being dispersed in a suitable synthetic resin binder for forming the thermal transfer layer. As such a synthetic resin binder, it is usually preferable to select a binder having high heat resistance and not hindering the transfer of the coloring material which occurs when heated. For example, the following binders are used. (1) Cellulosic resins Ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxycellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate and the like. (2) Vinyl resins polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl pyrrolidone, polyester, polyacrylamide and the like. Among the above synthetic resin binders, polyvinyl butyral resin or cellulose resin is preferable from the viewpoint of heat resistance and the like. In order to provide the thermal transfer layer 7 on the support 6, a coloring material and a synthetic resin binder are kneaded with a solvent or a diluent to form a thermal transfer layer coating composition, which is supported by an appropriate printing method or coating method. It may be provided on the body 6. In addition, if necessary, an optional additive may be added to the coating composition for a thermal transfer layer. Although the basic structure of the thermal transfer sheet is as described above, when the surface of the support is directly heated by a contact type heating means such as a thermal head, as shown in FIG. By providing a lubricating layer 8 containing a lubricant such as wax or a releasing agent on the side of the body 6 where the thermal transfer layer is not provided, fusion between a heating means such as a thermal head and a support is prevented and slippage is prevented. Can be good. The heat transfer sheet and the heat transfer sheet prepared as described above are superimposed on each other so that the heat transfer layer of the heat transfer sheet and the receiving layer of the heat transfer sheet come into contact with each other as shown in FIG. By applying thermal energy according to the image information to the interface of the receiving layer, the color material in the thermal transfer layer can be transferred to the receiving layer according to the thermal energy. EXAMPLE An ink composition for forming a receiving layer having the following composition was prepared, and a polyethylene terephthalate film (manufactured by Toray Co., Ltd.) having an A5 size (148 mm × 210 mm) and a thickness of 100 μm was prepared. Lumirror # 100) and dried to form a receiving resin layer. (Dry coating amount: 4.0 g / m ² ) Polyester resin: Vylon 200 (Toyobo) 1.0 part by weight Methyl ethyl ketone / toluene (weight ratio 1: 1) 9.0 parts by weight Next, a release agent layer ink composition having the following composition The product is applied to half the area of A6 size by the gravure printing method and dried,
A release agent layer was formed to obtain a heat transferable sheet. (Release agent layer thickness: about 0.1 μm). Amino-modified silicone: KF-393 (Shin-Etsu Chemical) 1.0 part by weight Epoxy-modified silicone: X-22-343 (Shin-Etsu Chemical) 1.0 part by weight Ethanol 25.0 parts by weight Isopropyl alcohol 23.0 parts by weight A thermal transfer sheet was prepared by preparing an ink composition for forming a thermal transfer layer having a composition, applying the composition on a 9 μm-thick PET with a heat-resistant treatment on the back surface so that the dry application amount was 1.0 g / m ² , and drying. Was. Disperse dye: KST-B-136 (Nippon Kayaku) 0.4 part by weight Ethyl hydroxyethyl cellulose (Hercules) 0.6 part by weight Methyl ethyl ketone / toluene (weight ratio 1: 1) 9.0 parts by weight of the obtained thermal transfer sheet The heat transfer layer and the heat transfer sheet obtained above are overlapped in a state where only the part where the release agent layer is formed in the heat transfer sheet facing each other, heated from the heat transfer sheet side by a thermal head, and printed, and then both sheets are printed. Upon peeling, the receiving layer and the transfer layer were easily peeled off, and no peeling of the transfer layer resin to the receiving layer occurred, showing good releasability. Next, when the thermal transfer printer TN5000 (Toshiba Corporation) was used to perform thermal transfer printing using wax on the remaining polyester resin layer alone, a clear black print was obtained, and the brushability was confirmed. Was. ００３４ ００３６ ００３６ ００３４ ００３７ ００３７ ００４９ ００４９ ００４９ ００４９ ００４４ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ ００４９ The thermal transfer sheet for preparing a transparent original according to the present invention has the above-mentioned structure, and is composed of a transparent base material and a transparent receiving layer provided thereon. By transferring a sheet using a thermal head or the like, the sheet can be used for an overhead projector, a slide projector, or the like, or used as a positive or negative for diazo copy or photolithography. Further, since the slip layer 8 is provided on the side of the support on which the thermal transfer layer is not provided, it is possible to prevent fusion between the heating means such as a thermal head and the support and to improve the slip.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a heat-transfer sheet for producing a transparent original according to the present invention. FIG. 2 is a cross-sectional view of a thermal transfer sheet. FIG. 3 is a cross-sectional view of a thermal transfer sheet. 1 is a cross-sectional view showing a state in which the thermal transfer sheet of FIG. 1 and the thermal transfer sheet for creating a transparent original are overlapped. [Description of References] 1 Thermal transfer sheet for creating a transparent original 2 Transparent substrate 3 Receptive layer 4 Release agent layer 5 Thermal transfer sheet 6 Support 7 Thermal transfer layer 8 Lubricious layer

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-158272 (JP, A) JP-A-59-190897 (JP, A) JP-A-54-36813 (JP, A) JP-A-58-158 148794 (JP, A) JP-A-59-165688 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] A heat transfer sheet for preparing a transmission original, which is used in combination with a heat transfer sheet having a dye layer containing a sublimable dye transferred by heating on one surface of the support and having a slip layer on the opposite surface of the support. A dye-fixing resin coating having a thickness of 2 to 10 μm, which receives a dye transferred from the thermal transfer sheet when heated on the transparent substrate, and has an average particle size of 10 to 100 μm, Specific surface area 2
Preparation of a transparent manuscript characterized in that a receiving layer containing 5 to 20% by weight of silica powder of less than 50 m ² / g is laminated, and a dye-permeable release agent layer is provided on a part of the receiving layer. Heat transfer sheet. 2. 2. A transparent manuscript according to claim 1, wherein said receiving layer is formed by providing a dispersion coating film comprising at least one resin and water on said base material and drying it. Heat transfer sheet.