JP2789300B2 - 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 photoengraving. The present invention relates to a heat transfer sheet for preparing a transparent original, which is suitable for producing a printed matter capable of performing the same, that is, 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. By the way, 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 200
C. for about one minute, but the printing condition of the thermal head is about several milliseconds at 400.degree. 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. SUMMARY OF THE INVENTION The present invention is directed to a thermal transfer for preparing a transparent original which is used in combination with a thermal transfer sheet provided with a dye layer containing a sublimable dye which is transferred by heating using a thermal head. A sheet, comprising a transparent plastic substrate and a dye-fixing resin coating layer receiving layer made of a polyester resin having a thickness of 2 to 10 μm, which receives a dye transferred from the thermal transfer sheet when heated. A dye-permeable, solid wax on the surface of the receiving layer,
The present invention relates to a heat-transferable sheet for producing a transparent original, which contains at least one of a fluorine-based or phosphate-based surfactant and a curable silicone oil. 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 comprises solid wax, fluorine-based Alternatively, a receiving layer 3 containing at least one release agent of a phosphate-based surfactant or a curable silicone oil is provided. As shown in FIG. 2, the heat transfer sheet 1 according to the second embodiment of the present invention has a receiving layer 3 provided on a base material 2 and a release agent on at least a part of the receiving layer 3. Layer 4 is provided and configured. This release agent layer 4
May be provided on the entire surface of the receiving layer 3, may be provided only on a part of the receiving layer 3 as shown in FIG. 3, or may be provided inside the receiving layer 3. May be contained. (Substrate) The substrate 2 has a role of holding the receiving 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.
m, preferably about 5 to 15 μm. (Receiving Layer) As described above, the receiving layer 3 of the heat transfer sheet 1 has a function of receiving a dye transferred from the thermal transfer sheet when heated, and specifically, as described below. 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) Polyurethane resin having an urethane bond, etc. (c) 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 heat transfer sheet 1 according to the first embodiment of the present invention.
Contains a dye-permeable release agent in the receiving layer 3 made of the resin as described above. As such a release agent, solid waxes, fluorine-based or phosphate-based surfactants, silicone oils, and the like are used. These compounds are added in advance to the resin forming the receiving layer, and the obtained resin mixture solution is applied to a substrate and dried to obtain the receiving layer. Each releasing agent will be specifically described below. [0010] The solid wax is preferably dispersed as fine particles in the resin forming the receptor layer 3, and therefore it is preferable that the solid wax is treated by a ball mill, a sand mill or the like before being added to the resin. As solid wax, polyethylene wax,
Amide wax, Teflon powder and the like are used.
This solid wax is contained in the resin in an amount of 5 to 5 times the weight of the resin.
It is added in an amount of 0% by weight, preferably 10-20% by weight. If the amount is less than 5% by weight, a sufficient releasing effect cannot be obtained, and the thermal transfer layer may be thermally bonded to the receptor layer.
On the other hand, if the amount exceeds 50% by weight, dyes transferred from the thermal transfer layer during heating cannot be sufficiently received.
Therefore, there are cases where the obtained image does not have sufficient resolution. A fluorine-based or phosphate-based surfactant is also added as a releasing agent to the resin forming the receptor layer. It is considered that a part of the surfactant added to the resin appears on the surface of the receiving layer, so that a releasing effect can be obtained. Such surfactants are specifically phosphate ester compounds such as Plysurf A
208S, Price Surf A210G, Price Surf DB
-01 (Daiichi Kogyo Pharmaceutical), Gaffac RS-41
0, Gaffac RA-600, Gaffac RE610
(Toho Chemical Industries, Ltd.), and fluorine-based surfactants include Unidyne DS501, Unidyne DS502 (Daikin Industries), FC430, FC431 (Sumitomo 3M) and the like. The surfactant is added to the resin in an amount of 0.5 to 10% by weight based on the weight of the resin. If the amount is less than 0.5% by weight, a sufficient releasing effect cannot be obtained. If the addition amount exceeds 10% by weight, the surface of the receiving layer becomes sticky and dust easily adheres to the surface, and when the transfer layer and the receiving layer come into contact with each other, the transfer layer can be heated without heating. Stains such as transfer of the dye to the receiving layer. [0012] Silicone oils are also added as a release agent to the resin forming the receiving layer. As the silicone oil, an oily oil can be used, but a curable oil is preferable. 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. When such a curable silicone oil is used as a release agent, the surface of the receiving layer becomes sticky or dust adheres, compared to the case of the surfactant-based release agent described above. And therefore can be used in large quantities. Curable silicone oils can be added to the resin in an amount of 0.5 to 30% by weight based on the weight of the resin.
If the addition amount is less than 0.5% by weight, a sufficient releasing effect cannot be obtained, and the thermal transfer layer may be thermally bonded to the receiving layer.
On the other hand, if the amount exceeds 30% by weight, the dye transferred from the thermal transfer layer at the time of heating cannot be sufficiently received, and the resulting image may not have a sufficient recording density. 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 the amino-modified silicone oil include KF-393, KF-857, and KF-85 manufactured by Shin-Etsu Chemical Co., Ltd.
8, X-22-3680, X-22-3801C, etc., while epoxy-modified silicone oils include KF-100T, KF-101, X-60-16
4, KF-103 and the like are used. As a catalyst or a photo-curable silicone oil, KS705F-PS
(Catalyst), KS705F-PS-1 (catalyst), KS-7
20, KS770-PL-3 (catalyst), KS774-P
L-3 and the like. Heat transfer sheet 1 according to a second embodiment of the present invention
As described above, the receiving layer 3 made of the resin is provided on the base material 2, and the releasing agent layer 4 is provided on at least a part of the receiving layer 3. The release agent layer 4 can be formed by dissolving or dispersing the aforementioned release agent in an appropriate solvent, applying the obtained solution or dispersion on the receiving layer 3, and then drying. The thickness of the release agent layer is 0.01 to 5 μm, preferably 0.0 to 5 μm.
It is preferably from 5 to 2 μm. If the thickness of the release agent layer is less than 0.01 μm, a sufficient release effect cannot be obtained. On the other hand, if it exceeds 5 μm, the dye permeability is impaired, which is not preferable. As described above, the release agent layer 4 may be provided on the entire surface of the receiving layer 3 or may be provided only on a part of the receiving layer 3. Generally, it is difficult to print an explanatory note or the like on the release agent layer, but it is possible to print on the receiving 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. A heat transfer sheet according to a third aspect of the present invention is characterized in that the above-described receiving layer contains fine silica powder. In the present invention, silica refers to silicon dioxide or a substance containing silicon dioxide as a main component. The fine powder 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:
AEROSILR972, AEROSIL 130, A
EROSIL 200, AEROSILOX50, AE
ROSIL TT600, AEROSIL MOX8
0, AEROSIL MOX170 (Aerosil Co., Ltd.)
(Silica powder manufactured by the company). 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 forming the receiving layer, and the obtained resin mixture solution is applied on a substrate and dried to form the 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. As such an additive, as one that enhances the releasability from the thermal transfer sheet,
A cured product of a silicone compound, such as a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil, may be used. Details of these modified silicone oils are as described above. Alternatively, as the receiving layer, a layer formed by providing a dispersion coating film comprising at least one kind of resin and water on a base material and then drying it may be used.
As a resin as a dispersoid constituting a dispersion with water,
(A) a resin having a single type of dyeing ability, (b) a mixture of the same type of resin having high and low dyeing ability, and (c) at least one type having a dyeing ability. However, a mixture of one or more resins that are mutually incompatible may be used. The dyeing ability of the resin depends on the properties of the resin,
In particular, it is considered to be substantially proportional to the glass transition temperature.
Generally, a resin having a glass transition temperature of -100 ° C to 20 ° C generally has a low dyeing ability, and a resin having a glass transition temperature of 40 ° C or higher generally has a 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 ester emulsion,
Polyvinyl acetate emulsion, ethylene / vinyl acetate copolymer emulsion, polystyrene emulsion, polyvinyl chloride emulsion, etc. (D) Aqueous dispersion of synthetic resin (aqueous dispersion of synthetic resin obtained by dispersing a synthetic resin solution or a melt of synthetic resin in water) Aqueous dispersion of polyester, aqueous dispersion of polyurethane, aqueous dispersion of polyethylene, 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 such that the resin component 2
0-70%, more preferably 30-60%, moisture 30-
80%, even more preferably in the range of 40-70%. Further, the dispersing agent is 0.1 wt.
-10%, more preferably 1-5%. 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. . As such an additive, a cured product of a silicone compound, such as a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil, may be mentioned as one that enhances the releasability from the thermal transfer sheet. 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. If necessary, a release layer may be formed on the surface of the receiving layer to enhance the releasability from the thermal transfer sheet. As a composition which forms such a release property, a cured product of a silicone compound such as a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil is preferably used. Details of these modified silicone oils are as described above. (Thermal Transfer Sheet) The thermal transfer sheet 1 as described above is used in combination with a thermal transfer sheet. As shown in FIG. 4, a typical thermal transfer sheet 5 has a configuration in which a thermal transfer layer 7 is provided on one side of a support 6 and the thermal transfer layer 7 is provided with a color contained therein when heated. The material is transferred onto the heat transfer sheet. As such a coloring material, about 1
Disperse dyes having a relatively small molecular weight of about 50 to 400, oil dyes, certain basic dyes, and intermediates which can be converted to these dyes, and the like, among them, thermal transfer temperature, thermal transfer efficiency, hue It is selected and used in consideration of color rendering properties, 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. EXAMPLES (Example 1) An ink composition for forming a receptor layer having the following composition was prepared, and was prepared to have a thickness of 1
A dry coating amount of 4.0 g / m on a 00 μm polyethylene terephthalate film (Lumilar # 100 manufactured by Toray Industries, Inc.)
² and dried to form a receiving layer. Polyester resin: Vylon 200 (Toyobo) 1.0 part by weight Methyl ethyl ketone / toluene (weight ratio 1: 1) 9.0 parts by weight Then, a solution for forming a release agent layer having the following composition was added to Myaba # 6.
Is applied on the polyester resin layer using
Dry at 0 ° C. for 5 minutes. 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 The release agent layer forming solution at this time has a dry coating amount of about 0.1
It was applied to be 5 g / m ² . Then, an ink composition for forming a thermal transfer layer having the following composition was prepared, and a dry coating amount of 1.0 g was applied to a 9-μm-thick PET whose back surface was subjected to heat treatment.
/ M ² and dried to obtain a thermal transfer sheet. Disperse dye: KST-B-136 (Nippon Kayaku) 0.4 part by weight tyl hydroxyethyl cellulose (manufactured by Hercules) 0.6 part by weight Methyl ethyl ketone / toluene (weight ratio 1: 1) 9.0 parts by weight The obtained thermal transfer sheet When the thermal transfer layer and the receiving layer of the heat-transferred sheet are superposed face to face, and heated from the thermal transfer sheet side with a thermal head to print, heat fusion of the thermal transfer layer to the receiving layer occurs. And showed good releasability, and the obtained product could be used as an original for an overhead projector. Example 2 A polyester solution having the same composition as in Example 1 was applied to the entire surface of an A5 size (148 mm × 210 mm) polyethylene terephthalate film (100 μm thick) and dried to form a receiving resin layer. . (Dry coating amount 4.0 g /
m ² ). Next, the release agent layer ink composition having the same composition as that of Example 1 was applied to a half area of A6 size by a gravure printing method and dried to form a release agent layer (release agent layer thickness: About 0.1 μm) Then, only on the part where the release agent layer was formed,
When sublimation transfer recording was performed in the same manner as in the above example, no peeling of the transfer layer occurred similarly in this case, and good releasability was exhibited. Then, a thermal transfer printer TN5000 (Toshiba Corporation) is applied to the remaining polyester resin layer only.
As a result, a clear black print was obtained and the brushability was confirmed, and the print was usable as an original for an overhead projector. The thermal transfer sheet for producing a transparent original according to the present invention has the above-mentioned structure and comprises a transparent base material and a transparent receiving layer provided thereon. By transferring the image with a thermal head or the like, the film 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, by using a polyester resin as the resin of the transparent receiving layer, a transparent and stable dye-fixing receiving layer can be obtained.

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 showing a heat transfer sheet for producing a transparent original according to the present invention. FIG. 4 is a cross-sectional view of a thermal transfer sheet for producing a transparent original. FIG. 4 is a cross-sectional view of a thermal transfer sheet. FIG. 5 is a cross-sectional view of a thermal transfer sheet. Cross-sectional view showing the combined state [Description of reference numerals] 1 Heat transfer sheet for preparing a transparent original 2 Transparent substrate 3 Receptive layer 4 Release agent layer 5 Thermal transfer sheet 6 Support 7 Thermal transfer layer 8 Slip layer

   ────────────────────────────────────────────────── ─── Continuation of front page                   (56) References JP-A-50-124718 (JP, A)                 JP-A-59-98897 (JP, A)                 JP-A-58-148794 (JP, A)                 JP-A-60-19138 (JP, A)

Claims (1)

(57) [Claims] A heat transfer sheet for creating a transparent original used in combination with a heat transfer sheet provided with a dye layer containing a sublimable dye that is transferred by heating using a thermal head, and a transparent plastic base material, when heated Thickness 2 to 10 for receiving dyes transferred from thermal transfer sheet
a receiving layer of a dye-fixing resin coating film made of a polyester resin having a thickness of μm, and a dye-permeable, solid wax, a fluorine-based or phosphate-based surfactant, or a curable silicone on the surface of the receiving layer. A heat-transferable sheet for producing a transparent document, characterized by containing at least one of oils. 2. 2. The heat transfer sheet according to claim 1, wherein the receiving layer contains silica powder having an average particle size of 10 to 100 [mu] m and a comparative surface area of less than 250 g / m < ² >. 3. 2. The method according to claim 1, wherein the receiving layer is formed by providing a dispersion coating film comprising at least one resin and water on the substrate and drying the coating. Heat transfer sheet.