JPH039878B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sublimation transfer type hard copy cover film suitable for being fused to the surface of a sublimation transfer type color hard copy photographic paper for color copying by sublimation transfer of a sublimation dye. Conventionally, one side of transfer paper printed with ink made using sublimable dyes is placed on surface-treated photographic paper, and the other side of the transfer paper is heated with a thermal head to remove the ink. It has been proposed to sublimate dyes and transfer dye them onto photographic paper to obtain color hard copies. A sublimation transfer color hard copy cover film is fused to the surface of this sublimation transfer color hard copy as a surface protective layer, so that, for example, when a hand touches the sublimation transfer type hard copy surface, the sublimation transfer color hard copy is removed from the hand. It is designed to prevent discoloration due to oils transferred to the hard copy surface. FIG. 1 shows an example of a conventional sublimation transfer color hard copy cover film as a whole. In FIG. 1, reference numeral 1 indicates a cover material, and this cover material 1 is supported by a base material 2 so as to form a sublimation transfer type color hard copy cover film 3 as a whole. Here, the cover material 1 is made of polyester resin (Vylon #200, manufactured by Toyobo Co., Ltd.) having a heat-adhesive property of about 5μ, and the base material 2
is made of a 12μ polyester film, and the cover material 1 is applied to the surface of the base material 2. Further, FIG. 2 shows another example of a conventional sublimation transfer type color hard copy cover film. In FIG. 2, parts corresponding to those in FIG. 1 are designated by the same reference numerals, and detailed explanation thereof will be omitted. In this example, the base material 2 is a 12μ polyester film.
A first layer 1a of the cover material made of cellulose acetate butyrate resin (Sumitomo Bayer) with a thickness of about 5μ is formed on top of the cover material, and a second layer 1a of the cover material with a thickness of about 5μ made of a polyester resin with heat fusion properties is formed on top of the first layer 1a of cellulose acetate butyrate resin (Sumitomo Bayer). 1b. By the way, in color hard copies made by dye transfer, although some of the dye is diffused into the surface treatment layer on the surface of the photographic paper, most of the dye is dyed in the form of aggregates. However, this caused problems because the dye did not sufficiently show its original color development. In addition, dyes with relatively good color development that are suitable for sublimation transfer printing are often found in disperse dyes, basic dyes, and solvent dyes, but when used as transfer paper, most of them are limited to disperse dyes and the number of dyes is small. Practically speaking, it is limited to a few dozen types. In order to obtain transfer paper suitable for color hard copies from among these limited dyes, the types of dyes are further limited when they are classified into the three primary colors cyan, magenta, and yellow, which are subtractive color mixtures. When we look at the hue of the dyes transferred and dyed onto treated photographic paper, the magenta color in particular often deviates to the red side, and therefore red, green, and blue, which are a mixture of the three primary colors of subtractive color mixture, are particularly red. However, there was a problem in that the color tended to be yellowish, that is, close to orange. For this reason, it is desirable to be able to arbitrarily control the color development of the reddish dye to the bluish side to achieve magenta color development, which is optimal for mixed color development. Incidentally, the present inventor has
The following experimental results were obtained regarding the color development of reddish dye when using the conventional sublimation transfer type cover film shown in the figure. First, for the first experiment, we used 24 parts by weight of saturated polyester resin (Pylon #200, manufactured by Toyobo Co., Ltd.) made by internally plasticizing photographic paper for sublimation transfer type color hard copies, and ultrafine silica (NIPSIL E220A, Nippon Silica Kogyo Co., Ltd.). A treatment solution consisting of 6 parts by weight of 6 parts by weight of a methyl ethyl ketone solvent was applied to one side of a piece of high-quality paper weighing 170 g/m ² so that the coating weight after drying was about 5 g/m ² . On the other hand, transfer paper for obtaining color hard copies as samples was prepared using 6 parts by weight of a reddish anthraquinone disperse dye with sublimation properties (PTR63, manufactured by Mitsubishi Chemical Corporation), 6 parts by weight of ethyl cellulose, and 88 parts by weight of isopropyl alcohol solvent.
Weigh magenta ink consisting of parts by weight 40g/m ²
It was formed by coating it on thin paper using a gravure coater so that the dry coating weight was 5 g/m ² . Next, a magenta color image was printed on the photographic paper using a heat-sensitive head at a temperature of around 300° C. from the back side of the transfer paper to obtain a sublimation transfer type color hard copy as a sample. Then, a color print was obtained by pressing the cover film 3 of the example shown in FIG. 1 on this sublimation transfer type color hard copy using a press plate heated to 150°C. For this experiment,
CIE (Com-mission International
Expressed by the chromaticity coordinate X value of the color system (de 1'Eclairage), it is 0.456, and it is necessary to control the color development of the reddish dye to the bluish side to produce a highly saturated magenta color. It was hot. Furthermore, this
The X value of the CIE color system means that the larger the value, the more red the color becomes, and the smaller the value, the more the blue color becomes the color. In addition, as a second experimental example, the cover film 3 of the example shown in FIG. 2
A color print with a sublimation transfer type cover film layer formed on the photographic paper was obtained. This second
CIE (Commission
Expressed in terms of the chromaticity coordinate X value of the International (International de 1'Eclairage) color system, it is 0.462, and the color development of the reddish dye is moderately controlled to the bluish side and adjusted to produce a highly saturated magenta color. I needed to. In view of the above, the present invention provides a cover film for sublimation transfer type hard copies that can control the coloring of reddish dye to a bluish side to produce a highly saturated magenta color and protect the surface of photographic paper. We aim to provide the following. The sublimation transfer type hard copy cover film of the present invention is a sublimation transfer type hard copy cover film that is fused to the surface of photographic paper, in which the cover film is made of a metal compound selected from Al, Mg, Ca, and Sn and a resin. It is characterized by containing a layer mainly composed of , and can arbitrarily control the color development of the reddish dye to the bluish side to produce a highly saturated magenta color and protect the surface of the photographic paper. It is something. Hereinafter, the sublimation transfer type color hard copy cover film of the present invention will be described in detail. In the cover film according to the present invention, a sublimable dye represented by polyester resin, epoxy resin, cellulose acetate resin, nylon resin, polyvinylpyrrolidone resin, etc. is mixed into a resin liquid mainly composed of a resin that is easily dyed and diffused. Among them, Al, Mg, Ca,
It contains a layer of heat-fusible adhesive obtained by dispersing or dissolving an organometallic compound selected from Sn, and when it is heat-fused onto photographic paper coated on one side of a heat-resistant base material, dye This is a cover film that can diffuse color and control magenta color. Here, as the metal compound used in the present invention, among metal compounds of Al, Mg, Ca, and Sn, those that can be dispersed or dissolved in the resin liquid to form a transparent adhesive layer are used. For example, organic acids such as oleic acid, naphthenic acid, stearic acid, and 2-ethylhexyl acid, metal salts of organic acids that are compounds of the above metals, alcohols such as ethyl alcohol, isopropyl alcohol, butyl alcohol, and 2-ethylhexyl alcohol, and Al. Examples include reaction products such as metal alcoholates such as aluminum isopropylate and aluminum butyrate, chelate compounds of acetylacetonate and metal such as aluminum acetonate, and aluminum oxide acylate compounds such as aluminum oxide stearate. Although there is no clear reason why the color development of the sublimable red dye according to the present invention can be controlled to a bluish hue, most of the red dyes with high sublimation dyeing properties are anthraquinone disperse dyes. In fact, the polar groups such as amino groups and hydroxyl groups in anthraquinone dyes and the activated metal atoms in the present invention are combined with the dyes diffused into the adhesive when the cover film is heated and fused onto the photographic paper, for example. This seems to be because the molecular bluish coloring material increases uniformly as a result of the instantaneous formation of chelate compounds and the like. In addition, although it is experimental that the concentration of such metal compounds is 0.1 to 30 PHR,
This is selected depending on the type of dye and the degree of color development, and is not particularly limited. Next, the results of experiments (Experimental Examples 1 to 4) conducted by the inventor of the present invention regarding the present invention will be explained. (Experimental Example 1) In this Experimental Example 1, the cover material 1 made of a polyester resin with heat-fusibility prepared in the conventional example shown in FIG. This is a layer in which diisopropylate (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) is dissolved. The other parts are constructed in the same manner as the sublimation transfer type color hard copy film shown in FIG. Then, this color hard copy film was heat-pressed in the same manner onto a sample color hard copy formed in the same manner as the example shown in FIG. 1 to obtain a color print. The X value of the CIE color system in this experimental example is
At 0.360, it is smaller than before, has an increased bluish tinge, and suppresses the reddish coloring of magenta. (Experimental Example 2) In this Experimental Example 2, the second layer (1b) of the cover material of the cover film for sublimation transfer type color copy prepared in the conventional example shown in FIG. against 10PHR aluminum oxide stearate (olive
It is formed by dissolving AOS (manufactured by Hope Pharmaceutical Co., Ltd.). The other parts are constructed in the same manner as the example shown in FIG. This sublimation transfer type color hard copy cover film is heat-pressed onto the sample color print in the same manner, and after the dye is diffused and colored, only the base material 2 made of polyester film is peeled off to form the sublimation transfer type cover film layer. formed. The X value of the CIE color system in this experimental example was 0.358, which was smaller than the conventional value, and the blue tint increased and the red tint of magenta was suppressed. (Experimental Example 3) In this Experimental Example 3, the cover material 1 of the above-mentioned example in Fig. & Film Co., Ltd.) is dissolved in a solution and dried to form a layer with a thickness of approximately 7μ when dry. The other parts are constructed in the same manner as the example in FIG. This sublimation transfer type color hard copy cover film was heat-pressed in the same manner onto a sample color hard copy to diffuse color development of the dye, and then only the base material 2 was peeled off to form a transfer cover film layer. The X value of the CIE color system in this experimental example was 0.372, which was smaller than the conventional value, and the blue tint increased and the red tint of magenta was suppressed. (Experiment Example-4) Let's explain Experiment Example-4 using FIG. 3.
In FIG. 3, parts corresponding to those in FIGS. 1 and 2 are given the same reference numerals, and detailed explanation thereof will be omitted. In FIG. 3, 2a indicates a capacitor paper having a thickness of 15 μm, and a heat-resistant coating layer 2b is provided on one side of this capacitor paper. This heat-resistant coating layer 2b is made of approximately 5μ of a resin liquid consisting of 21 parts by weight of urethane acrylate (XP7000B manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.), 9 parts by weight of epoxy acrylate (SP1509 manufactured by Showa Kobunshi Co., Ltd.), and 70 parts by weight of methyl ethyl ketone. After coating, this is coated with an electron beam in a nitrogen atmosphere to approx.
It is obtained by crosslinking with 10 Mrad irradiation. Also,
The first layer 1a of the cover material is formed from cellulose acetate propionate resin (manufactured by Sumitomo Bayer) with a thickness of about 5μ on the other side of this heat-resistant coating layer, and the second layer 1b of the cover material is formed with 8PHR of ethyl resin in the polyester resin. Acetoacetate aluminum diisopropylate (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.)
It shall be formed with a thickness of approximately 5 μm using a resin obtained by melting. On the other hand, this cover film was heat-pressed onto a sample color hard copy in the same manner as in the above-mentioned experimental example, and only the capacitor paper with the heat-resistant coating layer 2b was peeled off to form a transfer cover film layer on photographic paper. The X value of the CIE color system in this experimental example was 0.359, which was smaller than the conventional value, and the blue tint increased and the red tint of magenta was suppressed.

[Table] As mentioned above, when using the sublimation transfer type color hard copy cover film of the present invention, the table -
As is clear from the results of No. 1, there is an advantage that the X value is smaller than that of the conventional method, that is, the blue tint increases, and the red tint of magenta is suppressed. Furthermore, the blue tint development can be freely controlled by the type and amount of the metal compound mentioned in the present invention, and there is the advantage that the optimum magenta color can be obtained. Furthermore, since the cover film forms a protective layer for the dye, there is the advantage that the surface of the sublimation transfer type hard copy can be protected. The following may be further considered regarding the structure of the sublimation transfer type hard copy cover film of the present invention. The base material 2 can be a relatively heat-resistant plastic film base material with a smooth surface, such as polyester, polycarbonate, polyacrylate, etc., which has been subjected to pear treatment or peeling treatment as necessary, or a Either a two-layer structure as shown in Fig. 4 in which the above film is laminated on the paper surface as the first layer 2a, or a cross-linked heat-resistant resin liquid (e.g. silicone resin, unsaturated polyester resin, etc.) 2b is applied to ensure smoothness. It can be made with a raised base material.
The thickness of the base material 2 is 20 to 100μ, preferably 20 to 50μ
This can be selected in consideration of ease of handling, time required for hot pressing, etc. The cover material 1 is colorless and transparent and mainly consists of a thermoplastic resin layer that does not transmit ultraviolet rays and a metal compound that does not fuse with the base material but fuses with the photographic paper.The cover material 1 consisting of two layers 1a and 1b is the base material. The first layer on the side is a colorless and transparent cross-linked heat-resistant resin layer that does not fuse with the base material (for example, cross-linked urethane resin, cross-linked polyester resin, etc.), or a resin layer made mainly of a resin that does not transmit ultraviolet rays, such as acetate resin. The other layer can also be formed of a layer 1b mainly made of a colorless and transparent resin and a metal compound that has adhesive properties to the photographic paper and the upper layer 1a. The thickness of the cover material is 1 to 20 μ, preferably 5
~10μ is good. It is preferable to add a predetermined amount of ultraviolet absorber to the cover material to prevent ultraviolet rays. Since most sublimation dyes are disperse dyes, the surface of the photographic paper is treated with a resin that has high dyeability for disperse dyes, such as polyester, epoxy, or nylon, in order to improve dye dyeability. For 1b, it is necessary to select a resin that can be fused with these treated resins, but there is no particular limitation as long as the composition can be fused. The surface of the base material may be subjected to silicone-based or fluorine-based release treatment to facilitate release from the cover material. To block ultraviolet rays, a resin material that inherently does not allow ultraviolet rays to pass through may be used, or an ultraviolet absorber may be included in the cover material. Examples of the ultraviolet absorber include benzophenone-based ones such as hydroxybenzophenone and cyhydroxybenzophenone, benzotriazole-based ones, and salicylic acid derivatives. Further, the base material 2 may be left on the cover material 1 or 1b or peeled off if necessary. It should be noted that the present invention is not limited to the described examples such as the above-mentioned experimental examples, and it goes without saying that various other configurations can be made without departing from the gist of the present invention.

[Brief explanation of the drawing]

1 to 4 are diagrams for explaining the sublimation transfer hard copy cover film of the present invention. 1 is a cover material, and 2 is a base material.

Claims (1)

[Claims] 1. A transparent heat-fusible adhesive obtained by dispersing or dissolving an organometallic compound selected from Al, Mg, Ca, and Sn in a resin liquid that is mainly composed of a resin that is easily dyed and diffused by sublimable dyes. A sublimation transfer type hard copy cover film characterized by having a layer of an agent formed on one side of a heat-resistant base material.