JPS5976298A - Sublimation transfer type cover film - Google Patents

Abstract

PURPOSE:To provide the titled film for forming a magenta color with high saturation by controlling the color formation of a reddish dye to an arbitrary bluish side and capable of protecting the surface of photographic paper, obtained by containing a layer based on a specific metal compound and resin in a cover film. CONSTITUTION:A layer comprising a heat meltable adhesive obtained by dispersing or dissolving a compound of a metal selected from A, Mg, Ca and Sn in a resin solution based on resin in which a sublimable dye is easily deposited and diffused represented by polyester resin, epoxy resin and cellulose acetate resin is contained to obtain a cover film capable of diffusing and color devloping the dye when fused under heating to photographic paper formed by coating the single surface of a heat resistant substrate and controlling a magenta color. As the above-mentioned metal compound, substance capable of being dispersed or dissolved in the resin solution to form a transparent adhesive layer is used and, for example, a compound of an org. acid such as oleic acid and the above-mentioned metal is represented.

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 combined with surface-treated photographic paper.
It has been proposed to heat the transfer paper from the other side with a thermal head to sublimate the dye in the ink and transfer dye it onto the photographic paper to obtain a color hard copy.
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. 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 type color hard copy cover film as a whole.

In this FIG. 1, (1) indicates the cover material, and this -
The cover film (1) is supported by the base material (2), and the cover film (3) for sublimation transfer type color hard copy is used as a whole.
It is designed to form a Here, cover material (1)
is made of polyester resin (Pylon 200, manufactured by Toyobo Co., Ltd.) that has a thermal adhesiveness of approximately 5 μm, and the base material (2) has a heat-adhesive property of approximately 5 μm.
The cover coat (1) is applied to the surface of the base coat (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 given the same reference numerals, and detailed explanation thereof will be omitted.

In this example, 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 a base material (2) of a polyester film with a thickness of 12μ. The second layer (1b) of the cover material is formed with a thickness of approximately 5 μm and is made of a polyester resin with adhesive properties. 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, the majority of the dye is simply dyed in the form of aggregates. Because of this, there was a problem because the dye did not exhibit its original color development sufficiently. 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 hidden in disperse dyes and the number 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, so of the subtractive color mixture of red, green, and blue, especially red is yellow. There was a problem with the taste, that is, the coloration tended to be close to orange. For this reason, it was 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 obtained the following experimental results regarding the color development of reddish dye when using the conventional sublimation transfer type cover film shown in FIGS. 1 and 2 described above.

First, as a first experiment, we used saturated polyester resin (which is made by internally plasticizing photographic paper for sublimation transfer type color hard copies).
Byron 200. Toyobo Co., Ltd.) 24 parts by weight, ultrafine particles! J ty (NIPSIL E220A, manufactured by Nippon Silikani Gyo Co., Ltd.) 6 parts by weight, methyl ethyl ketone solvent 7
A treatment liquid containing 0 parts by weight was applied onto one side of a high-quality paper having a basis weight of 170 i/m 2 so that the coating weight after drying was approximately 5 f/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. A magenta color ink consisting of 1.5 mm was coated on thin paper with a basis weight of 40 mm to 7 mm using a gravure coater to give a dry coating weight of 5 F/m.sup.2. Next, a magenta color image was printed on the photographic paper using a thermal head at a temperature of about 300° C. from the back side of the transfer paper to obtain a sublimation transfer type color hard copy as a sample. Then, the cover film (3) of the example shown in FIG. 1 was pressed onto this sublimation transfer type color hard copy using a press plate heated to 150° C. to obtain a color print. In this experiment, the red color change was measured using CI E (Com
-m1ssion International de
Expressed by the chromaticity coordinate X value of the I Eclairage) color system, it is 0.456, and it is necessary to control the color development of the reddish dye to an appropriate bluish side to produce a highly saturated magenta color. there were. Incidentally, the X value of this CIE color system means that the larger the value, the more reddish the color becomes, and the smaller the value, the more blueish the color becomes.

In addition, as a second experimental example, the cover film (3) of the example shown in FIG.
Only the base material (2) of the polyester film was peeled off, and a sublimation transfer type cover film layer was formed on the photographic paper to obtain a color print. The red color change in this second experiment was measured by CIE (
Commission Inter-national
When expressed by the chromaticity coordinate X value of the color system (de 1' Eclairage), 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. There was a need.

In view of the above, the present invention is a sublimation transfer type hard copy cover film that can arbitrarily control the color development of reddish dye to a bluish side to develop 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, and the cover film contains At, Mg,
It is characterized by containing a layer mainly composed of a compound of a metal selected from Ca and Sn and a resin. It is capable of developing colors and preserving the surface of photographic paper.

Hereinafter, the sublimation transfer type color hard copy cover film of the present invention will be described in detail.

The cover film according to the present invention includes polyester film, epoxy resin, cellulose acetate resin, nylon resin,
Sublimable dyes such as polyvinylpyrrolidone resin are heated by dispersing or dissolving metal compounds such as At, Mg, Ca, and Sn in a resin solution that is easily dyed and diffused. It is a cover film that contains a layer of fusible adhesive, which is coated on one side of a heat-resistant base material, and when heated and fused onto photographic paper, allows the dye to diffuse and color and control the magenta color.

Here, the metal compounds used in the present invention include At,
Among the metal compounds of Mg, Ca, and Sn, those that can be dispersed or dissolved in a 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, phthyl alcohol, and 2-ethylhexyl alcohol, and At Examples include metal alcoholades such as aluminum isopropylate and aluminum butyrate, which are reaction products of aluminum, chelate compounds of acetylacetonate and metal such as aluminum acetonate, and aluminum oxide acylate compounds such as aluminum oxide stearate. The reason why the color development of the sublimable red dye according to the present invention can be controlled to a bluish hue is not clear, but it is because most of the red dyes with high sublimation dyeing properties are anthraquinone disperse dyes. The polar groups such as amino and hydroxyl groups in anthraquinone dyes and the activated metal atoms of the present invention are combined with the dyes diffused into the adhesive when heat-sealing the cover film onto photographic paper and, for example, chelate compounds. This seems to be due to the instantaneous formation of molecules, which uniformly increases the molecular bluish coloring material. Further, it is practical to set the metal compound to 0.1 to 30 PHR, but 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 conducted by the inventor of the present invention regarding the present invention (
Let's explain Experimental Example-1 to Experimental Example-4).

EXAMPLE In this Experimental Example-1, the cover material (1) made of polyester resin with heat-fusibility prepared in the conventional example shown in FIG.
The layer is prepared by dissolving aluminum ethyl acetoacetate diisopropylene (ALCH, manufactured by Yoken Fine Chemical Co., Ltd.). The other parts are constructed in the same manner as the sublimation transfer color notebook film shown in FIG. Then, this color hard copy film was
A color print was obtained by heating and pressing in the same manner onto a color hard copy sample formed in the same manner as in the illustrated example. The X value of the CIE color system in this experimental example was 0.360, which was smaller than the conventional one, and the blue tint increased and the red tint of magenta was suppressed.

EXAMPLE In this Experimental Example-2, the cover material 2/f4 (lb) of the cover film for sublimation transfer type color copy prepared in the conventional example shown in FIG. PHR aluminum oxide stearate (Olive AO8.

(Manufactured by Hope Pharmaceutical Co., Ltd.) is dissolved.

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 crystal phase (2) made of polyester film is peeled off, and the sublimation transfer type cover film is formed. A layer was formed. The X value of the CIE color system in this experimental example is 0
．． 358, which is smaller than the previous model, has an increased blue tinge, and suppresses the magenta red tinge.

EXAMPLE In this Experimental Example-3, the cover material (1) of the above-mentioned example in FIG.
pe'''Ca'', manufactured by Hope Pharmaceutical Co., Ltd.) 10PHR dissolved in a solution of polyvinylpyrrolidone (manufactured by General Aniline & Film Co., Ltd.) and dried.
It is formed as a layer of μ. 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 onto the sample color hard copy in the same manner, and after the dye was diffused and colored, 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 is 0.372
It is smaller than before, has an increased bluish tinge, and suppresses the magenta reddish color development.

Example This Experimental Example-4 will be explained 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) shows a capacitor paper with a thickness of 15 μm, and one side of this capacitor paper is provided with a heat-resistant coating layer (2b). This side thermal coating M (2b
) is urethane acrylate) (XP7000B manufactured by Nippon Gosei Chemical Industry Co., Ltd.) 21 parts by weight, epoxy acrylate)
(5P1509 manufactured by Showa Kobunshi ■) A resin solution consisting of 9 parts by weight of methyl ethyl ketofluoride and 0 parts of methyl ethyl ketofluoride is applied to about 5 μm, and then crosslinked by irradiation with an electron beam of about IQ Mrad in a nitrogen atmosphere. In addition, the first layer of cover material (1a)
is formed from cellulose acetate gropionate resin (manufactured by Sumitomo Bayer) on the other side of this heat-resistant coating layer, and the second layer (lb) of the cover material is made of polyester ().
(The film is formed with a resin of about 5 μm in thickness by dissolving 8 PHR of ethyl acetoacetate aluminum diisopropylate (ALCH1 manufactured by Kawaken Chemical Co., Ltd.).

On the other hand, this cover film was bonded under heat and pressure on the sample color hard copy in the same manner as in the above experimental example, and then a heat-resistant coating layer (
Only the capacitor paper with 2b) was peeled off to form a transfer cover film layer on the 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.

As mentioned above, when the sublimation transfer type force 2-hard copy cover film of the present invention is used, as is clear from the results in Table 1, the X value is smaller than that of the conventional method, that is, the bluish color increases. This has the advantage of suppressing the development of magenta reddish color. In addition, the bluish color development can be freely controlled by the type and amount of the metal compound mentioned in the present invention, and there is an advantage that the optimum magenta color can be obtained. In addition, since the cover film forms a protective layer for the dye, there is also the advantage that the sublimation transfer type hard copy surface can retain pus.

The following may be further considered regarding the structure of the sublimation transfer hard copy cover film of the present invention. The base material (2) can be a plastic film base with a smooth surface, such as polyester, polycarbonate, polyacrylate, etc., or a relatively heat-resistant plastic film base that has been subjected to pear treatment or peeling treatment as necessary. First layer of phase (2
Either create a two-layer structure as shown in Figure 4 by laminating the above film on the paper surface of a), or apply a cross-linked heat-resistant resin liquid (e.g. silicone resin, unsaturated polyester resin, etc.) (2b) to improve smoothness. This can be seen as increased profiteering.

The thickness of the base material (2) is 20 to 100μ, preferably 20μ
~50μ, which can be selected in consideration of ease of handling, time required for hot pressing, etc. Cover material (
1) is a cover material consisting of two layers (LA) and (LB), which is colorless and transparent and is mainly composed of a thermoplastic resin layer that does not transmit ultraviolet rays and a metal compound that does not fuse with profiteering paper but fuses with photographic paper.
In 1), one layer on the base material side is a colorless and transparent cross-linked heat-resistant resin layer (e.g. cross-linked urethane resin, cross-linked polyester resin, etc.) that does not fuse with the base material, but the main layer is a resin such as acetate resin that does not inherently transmit ultraviolet rays. The other layer may be formed of a layer (1b) mainly composed of a colorless and transparent resin and a metal compound that has adhesive properties to the photographic paper and the upper M (la). The thickness of the cover material is preferably 1 to 20 μm, preferably 5 to 10 μm. 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, and nylon, in order to improve dye dyeability. 1) or (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 a silicone-based or fluorine-based release treatment to facilitate release from the cover material. In order to block ultraviolet rays, it is possible to use a resin material that allows ultraviolet rays to pass through (although it is okay to use a resin material that does not allow ultraviolet rays to pass through).It is also possible to use a resin material that contains an ultraviolet absorber in the cover material. Benzophenone, dihydroxybenzophenone In addition to benzophenone-based products, there are benzotriazole-based products, salicylic acid derivatives, etc. Also, the base material (2) can be left on the cover material (1) or (1b) if necessary, but does not peel off. It is a good thing to do.

Note 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 adopted without departing from the gist of the present invention.

[Brief explanation of the drawing]

1 to 4 are diagrams for explaining the cover film for sublimation transfer notebook copying of the present invention. (1) is cover material, and (2) is profiteering. Hidemori Matsukuma 1) 1゛□

Claims (1)

[Claims] In a sublimation transfer type hard copy cover film that is fused to the surface of photographic paper, the cover film has Az, M
A cover film for a sublimation transfer type hard copy, comprising a layer mainly composed of a metal compound selected from G, Ca, and Sn and a resin.