JPH0542777A - Video photographic paper - Google Patents

Abstract

PURPOSE:To provide video photographic paper forming an image excellent in light fastness to its receiving layer by the transfer of a dye. CONSTITUTION:In video photographic paper wherein the dye or dye-containing ink supported on a support 2 is melted or sublimed by heating to be transferred to a receiving layer 3 mainly composed of a dye to form an image, the resin of the receiving layer 3 is mainly composed of polyvinyl alcohol or polyalkyl carbonate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a video printing paper,
In particular, it relates to a video photographic paper having a receiving layer consisting mainly of polyvinyl aryl or alkyl carbonate.

[0002]

2. Description of the Related Art Conventionally, an ink ribbon having a dye layer containing a sublimable disperse dye is used by a thermal head or the like.
Attempts have been made on a video printing paper to form an image composed of dyes transferred to the surface of a resin-coated paper by heating it in a dot shape according to an image signal. As shown in FIG. 1, the video printing paper is composed of a two-layer structure of a receiving layer 3 and a sheet-like base material 2. The receiving layer 3 is a dye that migrates from an ink ribbon, for example, a sublimable disperse dye. Is a layer for receiving (receiving) the image of (1) and maintaining the image formed by the receiving. Conventionally, polyester, polycarbonate, polyvinyl chloride copolymer and the like have been used as the material forming the receiving layer.

[0003]

However, the conventional video printing paper having the receptive layer made of these resins does not have sufficient light resistance and weather resistance of the formed image, and the sharpness of the formed image is lowered. It could be discolored or discolored.
It is considered that this is because the dye that is transferred by the thermal head or the like exists near the surface of the receiving layer and is therefore easily affected by light, humidity, oxygen in the air, and the like.

It is an object of the present invention to overcome the drawbacks of the prior art and to provide a video printing paper in which the image formed by dye transfer has excellent light and weather resistance.

[0005]

In order to achieve the above-mentioned object, the video printing paper of the present invention has a receptive layer to which the dye that has been melted or sublimated by heating is transferred, and transferred to the receptive layer. In a video printing paper on which an image is formed by the dye, the receiving layer contains polyvinyl carbonate.

The receiving layer is characterized in that it contains 50% by weight or less of another resin compatible with polyvinyl carbonate. Further, the receiving layer is characterized by containing a compound for enhancing the dyeing property.

The video printing paper according to the present invention is shown in FIG.
As shown in FIG. 5, the receiving layer 3 is formed on the sheet-shaped substrate 2. This video printing paper is used, for example, in combination with an ink ribbon having a dye layer containing a dye that melts or sublimates and transfers by heat, and the dye melted or sublimated by heating transfers to the receiving layer 3 mainly made of resin. As a result, an image is formed.

In the above video printing paper, the receptive layer is made of polyvinyl aryl carbonate or polyvinyl alkyl carbonate (polyvinyl phenyl carbonate, polyvinyl butyl carbonate, polyvinyl cyclohexyl carbonate, etc.) as a main material, so that the drawbacks of the prior art are solved. I was able to do it.

Although it was mentioned above that polycarbonate is used as the resin for the receiving layer, the name of this resin has the same part as the polymer of the present invention, and further attention is paid only to the "bonding group" of the polymer. If so, both of them belong to the category of "polycarbonate" and both may be confused with the same polymer. Therefore, the difference between the polycarbonate conventionally used here and the resin used in the present invention is explain.

In the resin generally called "polycarbonate", the main chain of the molecule is carbonic acid ester (Carbo in English).
Nate) linear polymer having the general formula shown in Chemical formula 1.

[0011]

[Chemical 1]

R ¹ of the practically used resin is a general-purpose resin which usually comprises an aromatic nucleus (aryl group) and is produced by a condensation reaction between a dihydric phenol and phosgene or the like. On the other hand, the polyvinyl aryl carbonate or polyvinyl alkyl carbonate in the present invention belongs to the vinyl polymer represented by the general formula shown in Chemical formula 2.

[0013]

[Chemical 2]

There are no reports on this polymer.
(However, in the present invention, since the vinyl carbonate monomer is difficult to synthesize, it was synthesized by reacting polyvinyl alcohol with an aryl or alkylchloroformate ester). As described above, although they are similar in name, they are completely different in basic knowledge and classification of polymer chemistry, and the polymer of the present invention and the conventionally known polycarbonate are completely different from each other. By using polyvinyl aryl carbonate or polyvinyl alkyl carbonate having the structure of 2, it is possible to obtain a light-resistant and weather-resistant receiving layer. When R ² is an alkyl group in Chemical formula ² , the number of carbon atoms is 1 to 1.
8 is preferable, and when it is an aryl group,
The number of carbon atoms is preferably 1-5. The degree of polymerization is preferably 300 or more, more preferably 500 or more.

Polyvinyl aryl carbonate or polyvinyl alkyl carbonate is produced by reacting polyvinyl alcohol with aryl chloroformate or alkyl chloroformate, and various kinds of polyvinyl aryl carbonate or polyvinyl alkyl carbonate can be selected by selecting a reaction raw material. Can be manufactured.

As a raw material, for example, as an aryl compound, phenyl chloroformate, 2-naphthyl chloroformate, o-toluyl chloroformate,
There are p-toluyl chloroformate, p-isopropylphenyl chloroformate, p-phenylphenyl chloroformate aryl and the like, and as the alkyl compound, methyl chloroformate, ethyl chloroformate, n-butyl chloroformate. Acid ester, isobutyl chloroformate, amyl chloroformate, hexyl chloroformate, octyl chloroformate,
Examples thereof include cetyl chloroformate, chloroethyl chloroformate, methoxyethylene chloroformate, benzyl chloroformate, and p-nitrobenzyl trichloroethyl chloroformate. As polyvinyl alcohol, there are polymers having a changed saponification degree or viscosity (polymer), such as Gohsenol (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., polyvinyl alcohol, there are dozens of typical products). Can be mentioned. Needless to say, the above-mentioned compounds are merely representative ones, and the compounds as the raw materials used in the present invention are not limited thereto.

Esters, ethers, and hydrocarbon compounds are compounds that are compatible with polyvinyl aryl carbonates or polyvinyl alkyl carbonates, increase dyeing properties of dyes, and act as additives for improving light resistance and heat resistance. There are various compounds such as, and the compounds exemplified below are merely examples. It is considered that these compounds are compatibilized with polyvinyl aryl or alkyl carbonates to promote the diffusibility of the dye, and have a function of permeating the dye into the inside of the receiving layer. For example, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dioctyl adipate, dioctyl separate, aliphatic dibasic acid esters such as dicyclohexyl azelate, triphenyl phosphate, Tricyclohexyl phosphate, phosphoric acid esters such as triethyl phosphate, further dimethyl isophthalate, diethyl isophthalate, isophthalic acid esters such as dicyclohexyl isophthalate, butyl stearate, higher fatty acid ester such as cyclohexyl laurate, tetraethyl silicate, Silicate esters such as tetraphenyl silicate, borate ester such as tributyl borate, triphenyl borate, etc. S, diphenyl carbonate, dicyclohexyl carbonate, phenyl carbonate, and the like carbonates such as diphenyl carbonate.

As the ethers, diphenyl ether,
Examples of hydrocarbon compounds such as dicyclohexyl ether and methyl ester of p-ethoxybenzoic acid include camphor,
Examples thereof include low-molecular polystyrene, phenols such as p-phenylphenol and o-phenylphenol, and sulfonic acid amides such as N-ethyltoluenesulfonic acid amide.

Mixtures of polyvinyl aryl carbonates or polyvinyl alkyl carbonates with other resins can also form the receiving layer. For example, the resins shown below can be used alone or as a mixture of several kinds, but the resins are not limited to the resins shown below, and the following are merely specific examples. (A) Those having an ester bond.

Polyester resin, polyacrylic ester resin, polycarbonate resin, polyvinyl acetate resin,
Styrene acrylate resin, vinyl toluene acrylate resin. (B) having a urethane bond. Polyurethane resin etc.

(C) A compound having an amide bond. Polyamide resin. (D) A compound having a urea bond. Urea resin etc. (C) Other.

Polycaprolactone resin, polystyrene resin, polyvinyl chloride and its copolymer, polyacrylonitrile and its copolymer.

As the saturated polyester, for example, Byron 200, Byron 290, Byron 600, etc. (all manufactured by Toyobo Co., Ltd.), UE3600, XA6098, XA702.
6 (above, Unitika Ltd.), TP220, TP235
(Above, manufactured by Nippon Gosei Co., Ltd.) and the like are used. Examples include aromatic dibasic acids and glycols, aliphatic dibasic acids and glycols, aromatic and basic acids, and mixed polyesters of aliphatic dibasic acids and glycols. Urethane resins include ether-type polyurethanes and ester-type polyurethanes made from polyethers or polyesters having a hydroxyl group at the molecular end and isocyanate, and resins having amide bonds such as nylon and diamines having branched groups. There are polyamides derived from dimer acid and the like. As the compound having a urea bond, in addition to the compound obtained by the reaction of diamine acid and diisocyanates, a reaction product of urea and aldehydes can be used. Further, a wide range of materials such as polycaprolactone having an ester bond, polystyrene, vinyl chloride and its copolymer, and polyacrylonitrile copolymer can be used.
The vinyl chloride / vinyl acetate copolymer which is a vinyl chloride copolymer preferably has a vinyl chloride component content of 85 to 97% by weight and a degree of polymerization of about 200 to 800. In addition, those containing a vinyl alcohol component, a maleic acid component and the like are also effective.

When the polyvinyl aryl carbonate or polyvinyl alkyl carbonate is used in combination with another resin, 1 to 100 parts by weight of the other resin can be used with respect to 100 parts by weight of the polyvinyl aryl carbonate or polyvinyl alkyl carbonate.

On the other hand, in order to improve the whiteness of the receptive layer to enhance the clarity of the transferred image, to give the image surface writability, and to prevent retransfer of the transferred image, the receptive layer 3 has fluorescence. Whitening agents and white pigments can be added. As the optical brightener, many compounds commercially available as optical brighteners such as Ubitex OB manufactured by Ciba-Gigi Co., Ltd. can be used. Examples of the white pigment include titanium oxide, zinc oxide, kaolin, clay, calcium carbonate and fine powder silica, which can be used alone or in combination of two or more kinds. Further, in order to improve the light resistance of the transferred image, one or more kinds of additives such as an ultraviolet absorber, a light stabilizer, an antioxidant and the like can be added to the receptor layer if necessary. The amount of these fluorescent whitening agents, white pigments, ultraviolet absorbers, light stabilizers, etc. added is 0. 0 with respect to 100 parts by weight of polyvinyl aryl carbonate or polyvinyl alkyl carbonate.
05 to 10 parts by weight is suitable, but depending on the purpose, an amount outside the range may be added, and the above-mentioned addition amount is merely an example thereof, and therefore, the addition amount is restricted. Not something.

The video printing paper of the present invention may contain a releasing agent in the receiving layer in order to improve the releasing property from the ink ribbon sheet. Examples of the releasing agent include solid waxes such as polyethylene wax, amide wax and Teflon powder, fluorine-based and phosphoric acid ester-based surfactants, silicone oil, and high melting point silicone wax, with silicone oil being preferred.

For example, the silicone oil may be oily or reaction (curing) type, and may be used depending on the purpose. Examples of the reaction (curing) type silicone include alcohol-modified silicone oil and isocyanate. Further, as the reaction (curing) type silicone oil, an epoxy-modified silicone oil (epoxy / polyether-modified silicone oil) and a carboxy-modified silicone oil (carboxy / polyether-modified silicone oil) are reaction-cured, or an amino-modified silicone. Those obtained by reaction-curing oil (amino / polyether-modified silicone oil) and carboxy-modified silicone oil (carboxy / polyether-modified silicone oil) are also preferable. The thickness of the release agent layer is 0.01 to
The thickness is preferably 5 μm, but is not particularly limited to this thickness.

In order to suppress the generation of static electricity during the processing of the video printing paper or during running in the printer, an antistatic agent may be contained in the polyvinyl aryl or alkyl carbonate type receiving layer or on the surface of the receiving layer.
As the antistatic agent, a surface active agent such as a cationic surface active agent (eg, quaternary ammonium salt, polyamine derivative, etc.), an anionic surface active agent (eg, alkylbenzene sulfonate, alkyl sulfate sodium salt), zwitterionic type Examples thereof include surfactants and nonionic surfactants.

These antistatic agents may be formed by coating on the surface of the receptor layer or added to polyvinyl aryl carbonate or polyvinyl alkyl carbonate.

[0030]

When a polyvinyl aryl carbonate or polyvinyl alkyl carbonate type resin is used as the main component of the receiving layer 3, a polyester which has been conventionally used,
Compared with the case of using a polycarbonate resin or the like, the light resistance is improved, and the dyeing property is improved by blending a compound that enhances the dyeing property to the polyvinyl aryl carbonate or polyvinyl alkyl carbonate resin. .. Further, the light resistance is further improved by blending the polyvinyl aryl or alkyl carbonate resin with another resin.

[0031]

EXAMPLES Preferred examples of the present invention will be described below based on experimental results.

Resin Synthesis First, a resin as a material for the receiving layer of the receiving layer sheet was synthesized. Hereinafter, a method for producing polyvinyl phenyl carbonate will be described as a typical example of the method for producing polyvinyl carbonate.

A 500 ml four-necked flask equipped with a stirrer, a temperature system, a dropping funnel, a backflow condenser (equipped with a calcium chloride tube on the upper part) and a nitrogen gas introduction tube was set on a mantle heater, and polyvinyl alcohol (Japan Synthetic Chemical Industry Co., Ltd., trade name Gohsenol NM-11, viscosity 13-
16, saponification degree 99.0 or more, volatile content 5% or less, ash content 0.7% or less, PH5-7) 8.8 g (stored in a desiccator containing silica gel for 1 week) and pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) , 30 ml of special reagent grade and 250 ml of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) are charged, and the mixture is gently stirred at room temperature for 24 hours while introducing nitrogen gas. Then, 47 g of phenyl chloroformate from the dropping funnel
Is dripped. A white insoluble matter is formed at the same time as the dropping, and the temperature of the content liquid rises. Adjust the dropping rate of chloride to adjust the liquid temperature to 8
Keep below 0 ° C. The whole amount of chloride is added, and after the liquid temperature becomes constant, the mixture is heated, the liquid temperature is set to 100 ° C., and the reaction is performed as it is for 10 hours. During this time, the white precipitate becomes powdery and the liquid turns red. After stopping the heating and allowing the contents to cool to room temperature, the mixture is dripped into 80% methanol water that is vigorously stirred. A white precipitate is formed at the same time as the dropping.
The precipitate is filtered off, washed several times with methanol until chlorine ions are not observed during washing, and dried under reduced pressure (10 mmHg,
50 ° C., 48 hours).

The reaction product dissolves in methyl ethyl ketone and acetic ester at room temperature and in toluene and cyclohexanone when heated. Methyl ethyl ketone solution (concentration 0.5
(100 g / 100 ml) has an intrinsic viscosity of 1.98, and the infrared absorption spectrum of the film (prepared from a methyl ethyl ketone solution) shows 1770 cm ⁻¹ , 1220 c.
The absorption of the carbonate-bonded carbonyl group near m ⁻¹ ,
The absorption of the monosubstituted aromatic compound is clearly shown around 700 cm ^-1 . Furthermore, the saponification value of carbonate bond (FDS
nell, L .; S. Effre, Encycl, In
d. chem. ANAL, 17, p330 (197)
3), Interscience Publ. The reaction rate of the hydroxyl groups of polyvinyl alcohol obtained from () was 86%. From the above measurement results and raw materials, in this reaction product, 86% of the polyvinyl alcohol hydroxyl groups are present as phenyl carbonate groups, and 14% are present as unreacted. It is presumed to be a polyvinyl phenyl carbonate / vinyl alcohol copolymer. The reaction rate of the polyvinyl alcohol hydroxyl group is preferably 50% or more from the viewpoint of solubility in an organic solvent and physical properties of the film.

Preparation of Receiving Sheet For the receiving sheet, a receptive layer composition was dried on a synthetic paper (trade name: FPG-150, manufactured by Oji Yuka Co., Ltd.) having a thickness of 10 μm.
It was prepared by coating so as to have a thickness of m and curing at 50 ° C. for 48 hours. The composition of the receiving layer composition is shown below. Table 1 shows the type of resin and the composition amount of the compound for enhancing the dyeing property in each sheet.

Receptor layer composition Resin 20.0 parts by weight (see Table 1) Compound for improving dyeability 0 to 4 parts by weight (see Table 1) Isocyanate 1.0 parts by weight (Takeda Yakuhin, trade name Takenate D-110N) Modified silicone oil 0.6 parts by weight (Toray Dow Corning, trade name SF8427) Optical brightener 0.04 parts by weight (Ciba Geigy, trade name Ubitex OB) Methyl ethyl ketone 40.0 parts by weight

[0037]

[Table 1]

Ink Ribbon Used In this example, the following dyes were used as the ink layer forming composition. (1) Methine dye (A) (Macrolex Yel
low 6G Bayer Co., Ltd. (2) Methine dye (B) (Foron Brilli)
ant Blue SR-PI Sandoz Co., Ltd.) (3) Anthraquinone dye (C) (Macrolex)
Red VioletR Bayer) (4) Azo dye (D) (Sumikaron Red)
S-BDF Sumitomo Chemical Co., Ltd. (5) Indoaniline dye (E) (6) Yellow (printing material ribbon VPM-30ST
Sony) Magenta (Printing material ribbon VPM-30ST Sony Corporation) Cyan (Printing material ribbon VPM-30ST Sony Corporation) (7) Yellow (Printing material ribbon UPC-3010)
Sony Corporation) Magenta (Printing Material Ribbon UPC-3010 manufactured by Sony Corporation) Cyan (Printing Material Ribbon UPC-3010 manufactured by Sony Corporation) Here, the structural formula of (5) indoaniline dye (E) is shown in Chemical formula 3. It is shown.

[0039]

[Chemical 3]

The method for synthesizing this dye is as follows. First, to synthesize an indoaniline derivative,
2- (n-butyroylamino) -4,6-dichloro-5
Dissolve 3 g of methylphenol in 200 g of ethanol,
A solution prepared by dissolving 8 g of sodium carbonate in 100 g of water was added thereto and stirred well. There, 4-amino-N (β-hydroxyethyl) -N-ethyl-m-toluidine sulfate 5
g was dissolved in 100 g of water and stirred for 30 minutes, 15 g of sodium hypochlorite solution was added little by little, and when the addition was completed, stirred for 10 minutes, 300 g of water was added and filtered to obtain dye crystals. .. The reaction formula is shown in Chemical formula 4.

[0041]

[Chemical 4]

Then, 2 g of the crystals of the dye thus obtained was dissolved in 50 g of pyridine, 0.6 g of butyryl chloride was added little by little, and the mixture was refluxed for 1 hour for esterification. Equation 5 shows a reaction formula.

[0043]

[Chemical 5]

The obtained compound was purified by column chromatography (filler: Wako Pure Chemical Industries, Ltd., trade name Wakogel C-200) using chloroform as a developing solvent. Next, an ink layer composition containing a dye was prepared according to the following composition. Ink layer composition Dye 3.70 parts by weight Ethyl hydroxyethyl cellulose 7.42 parts by weight (EHEC-LOW Hercules) Toluene 44.44 parts by weight Methyl ethyl ketone 44.44 parts by weight

An ink was prepared by stirring the mixture having the above composition. Then, a dry film thickness of about 1 μm was formed on a 6 μm polyethylene terephthalate (PET) film which was back-treated with a coil bar from the ink layer composition.
To obtain a sublimation transfer sheet, which was used as an ink sheet. Using the ink sheet prepared as described above, thermal transfer recording was carried out on the receiving layer sheet to be the transferred body.

Thermal transfer recording In thermal transfer recording, an ink sheet and a receiving layer sheet are printed on a color video printer (manufactured by Sony Corporation, trade name CVP-G50).
0) was used to carry out 12-step gradation printing.

[0047] 60,000KJ / m ² was irradiated with the light resistance test floor signed image the receiving layer sheet xenon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.). Macbeth reflection densitometer (TR-
924 type), the highest density part and the gradation part near the density of 1.0 were measured, and the residual ratio of the dye was calculated according to the following formula.

Residual rate of dye (%) = density after xenon irradiation / density before xenon irradiation × 100

Dark Fading Test Gradation-printed receptor layer sheet was kept in a thermo-hygrostat (Tabay) at 65 ° C. and relative humidity of 85% for 10 days, and a Macbeth reflection densitometer (TR-924) was used. The density change before and after the test at the highest density part and near 1.0 was measured, and the residual ratio of the dye was calculated according to the following formula.

Residual rate of dye (%) = density after test / density before test × 100

Dyeing Density Measurement Using a Macbeth reflection densitometer (TR-924), the highest density portion of the gradation-printed receiving layer sheet was measured. The results of dyeing density, light resistance test and dark fading test of printed images using the polymer of the present invention as a receiving layer are shown in Table 2 and Table 3 together. In the table, Y is a yellow dye, M is a magenta dye,
C represents a cyan dye.

[0052]

[Table 2]

[0053]

[Table 3]

From the test results shown in Tables 2 and 3, the dyeing degree was improved by using the polymer of the present invention as compared with the conventionally used polyester resins (Comparative Examples 1 and 2).
Light resistance, high residual ratio of dye after fading test, light resistance,
It can be seen that durability such as discoloration resistance is improved.

The present invention is not limited to the above-mentioned embodiments, and it goes without saying that various other configurations can be adopted without departing from the gist of the present invention.

[0056]

INDUSTRIAL APPLICABILITY In the present invention, since a polyvinyl aryl or alkyl carbonate type resin is used as the resin for the receiving layer, it is compared with the case where a polyester type resin generally used as the receiving layer resin is used. Then, the dyeing property and the light resistance are improved, and the dyeing property and the light resistance can be improved by blending a compound that enhances the dyeing property to the polyvinyl aryl or alkyl carbonate resin. Further, by blending the polyvinyl aryl or alkyl carbonate resin with another resin, there is an advantage that the performance may be further improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a video printing paper.

[Explanation of symbols]

 1 Video printing paper 2 Sheet-like substrate 3 Receptive layer

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a video printing paper,
In particular, it relates to a video photographic paper having a receiving layer consisting mainly of polyvinyl aryl or alkyl carbonate.

[0002]

2. Description of the Related Art Conventionally, an ink ribbon having a dye layer containing a sublimable disperse dye is used by a thermal head or the like.
Attempts have been made on a video printing paper to form an image composed of dyes transferred to the surface of a resin-coated paper by heating it in a dot shape according to an image signal. The video printing paper is composed of a two-layer structure of a receptive layer and a sheet-like substrate, and the receptive layer receives (receives) an image of a dye that migrates from the ink ribbon, for example, a sublimable disperse dye. It is a layer for maintaining the image formed by. Conventionally, as the material constituting the receiving layer, polyester, polycarbonate,
Polyvinyl chloride copolymer and the like have been used.

[0003]

However, the conventional video printing paper having the receptive layer made of these resins does not have sufficient light resistance and weather resistance of the formed image, and the sharpness of the formed image is lowered. It could be discolored or discolored.
It is considered that this is because the dye that is transferred by the thermal head or the like exists near the surface of the receiving layer and is therefore easily affected by light, humidity, oxygen in the air, and the like. It is an object of the present invention to overcome the deficiencies of the prior art and to provide a video photographic paper in which the image formed by dye transfer has excellent light and weather resistance.

[0004]

In order to achieve the above-mentioned object, the video printing paper of the present invention has a receptive layer to which the dye that has been melted or sublimated by heating is transferred, and transferred to the receptive layer. In a video printing paper on which an image is formed by the dye, the receiving layer contains polyvinyl carbonate. Further, the receiving layer is characterized by containing another resin compatible with polyvinyl carbonate in an amount of 50% by weight or less. Further, the receiving layer is characterized by containing a compound for enhancing the dyeing property.

The video printing paper according to the present invention is shown in FIG.
As shown in FIG. 5, the receiving layer 3 is formed on the sheet-shaped substrate 2. This video printing paper is used, for example, in combination with an ink ribbon having a dye layer containing a dye that melts or sublimates and transfers by heat, and the dye melted or sublimated by heating transfers to the receiving layer 3 mainly made of resin. As a result, an image is formed.

In the above video printing paper, the receptive layer is composed of polyvinyl aryl carbonate or polyvinyl alkyl carbonate (polyvinyl phenyl carbonate, polyvinyl butyl carbonate, polyvinyl cyclohexyl carbonate, etc.) as a main material, thereby eliminating the drawbacks of the prior art. I was able to do it.

It was mentioned above that polycarbonate is used as the resin for the receiving layer. However, the name of this resin has the same part as the polymer of the present invention, and further attention is paid only to the "bonding group" of the polymer. If so, both of them belong to the category of "polycarbonate" and both may be confused with the same polymer. Therefore, the difference between the polycarbonate conventionally used here and the resin used in the present invention is explain.

The resin generally called "polycarbonate" has a main chain of carbonic acid ester (Carbo in English).
Nate) linear polymer having the general formula shown in Chemical formula 1.

[0009]

[Chemical 1]

R ¹ of the practically used resin is a general-purpose resin which usually comprises an aromatic nucleus (aryl group) and is produced by a condensation reaction between a dihydric phenol and phosgene. On the other hand, the polyvinyl aryl carbonate or polyvinyl alkyl carbonate in the present invention belongs to the vinyl polymer represented by the general formula shown in Chemical formula 2.

[0011]

[Chemical 2]

There are no reports on this polymer.
(However, in the present invention, since the vinyl carbonate monomer is difficult to synthesize, it was synthesized by reacting polyvinyl alcohol with an aryl or alkylchloroformate ester). As described above, although they are similar in name, they are completely different in basic knowledge and classification of polymer chemistry, and the polymer of the present invention and the conventionally known polycarbonate are completely different from each other. By using polyvinyl aryl carbonate or polyvinyl alkyl carbonate having the structure of 2, it is possible to obtain a light-resistant and weather-resistant receiving layer. When R ² is an alkyl group in Chemical formula ² , the number of carbon atoms is 1 to 1.
8 is preferable, and when it is an aryl group,
The number of carbon atoms is preferably 1-5. The degree of polymerization is preferably 300 or more, more preferably 500 or more.

Polyvinyl aryl carbonate or polyvinyl alkyl carbonate is produced by the reaction of polyvinyl alcohol with aryl chloroformate or alkyl chloroformate, and various kinds of polyvinyl aryl carbonate or polyvinyl alkyl carbonate can be selected by selecting a reaction raw material. Can be manufactured.

As the raw material, for example, as an aryl compound, phenyl chloroformate, 2-naphthyl chloroformate, o-toluyl chloroformate,
There are p-toluyl chloroformate, p-isopropylphenyl chloroformate, p-phenylphenyl chloroformate aryl and the like, and as the alkyl compound, methyl chloroformate, ethyl chloroformate, n-butyl chloroformate. Acid ester, isobutyl chloroformate, amyl chloroformate, hexyl chloroformate, octyl chloroformate,
Examples thereof include cetyl chloroformate, chloroethyl chloroformate, methoxyethylene chloroformate, benzyl chloroformate, and p-nitrobenzyl trichloroethyl chloroformate. As polyvinyl alcohol, there are polymers having a changed saponification degree or viscosity (polymer), such as Gohsenol (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., polyvinyl alcohol, there are dozens of typical products). Can be mentioned. Needless to say, the above-mentioned compounds are merely representative ones, and the compounds as the raw materials used in the present invention are not limited thereto.

Esters, ethers, and hydrocarbon compounds are compounds that are compatible with polyvinyl aryl carbonates or polyvinyl alkyl carbonates, increase dyeing properties of dyes, and act as additives for improving light resistance and heat resistance. There are various compounds such as, and the compounds exemplified below are merely examples. It is considered that these compounds are compatibilized with polyvinyl aryl or alkyl carbonates to promote the diffusibility of the dye, and have a function of permeating the dye into the inside of the receiving layer. For example, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dioctyl adipate, dioctyl separate, aliphatic dibasic acid esters such as dicyclohexyl azelate, triphenyl phosphate, Tricyclohexyl phosphate, phosphoric acid esters such as triethyl phosphate, further dimethyl isophthalate, diethyl isophthalate, isophthalic acid esters such as dicyclohexyl isophthalate, butyl stearate, higher fatty acid ester such as cyclohexyl laurate, tetraethyl silicate, Silicate esters such as tetraphenyl silicate, borate ester such as tributyl borate, triphenyl borate, etc. S, diphenyl carbonate, dicyclohexyl carbonate, phenyl carbonate, and the like carbonates such as diphenyl carbonate.

As the ethers, diphenyl ether,
Examples of hydrocarbon compounds such as dicyclohexyl ether and methyl ester of p-ethoxybenzoic acid include camphor,
Examples thereof include low-molecular polystyrene, phenols such as p-phenylphenol and o-phenylphenol, and sulfonic acid amides such as N-ethyltoluenesulfonic acid amide.

Mixtures of polyvinyl aryl carbonates or polyvinyl alkyl carbonates with other resins can also form the receiving layer. For example, the resins shown below can be used alone or as a mixture of several kinds, but the resins are not limited to the resins shown below, and the following are merely specific examples.

(A) Those having an ester bond. Polyester resin, polyacrylic ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin. (B) having a urethane bond. Polyurethane resin etc. (C) Those having an amide bond. Polyamide resin. (D) A compound having a urea bond. Urea resin etc. (C) Other. Polycaprolactone resin, polystyrene resin, polyvinyl chloride and its copolymer, polyacrylonitrile and its copolymer.

As the saturated polyester, for example, Byron 200, Byron 290, Byron 600, etc. (all manufactured by Toyobo Co., Ltd.), UE3600, XA6098, XA702.
6 (above, Unitika Ltd.), TP220, TP235
(Above, manufactured by Nippon Gosei Co., Ltd.) and the like are used. Examples include aromatic dibasic acids and glycols, aliphatic dibasic acids and glycols, aromatic and basic acids, and mixed polyesters of aliphatic dibasic acids and glycols. Urethane resins include ether-type polyurethanes and ester-type polyurethanes made from polyethers or polyesters having a hydroxyl group at the molecular end and isocyanate, and resins having amide bonds such as nylon and diamines having branched groups. There are polyamides derived from dimer acid and the like. As the compound having a urea bond, in addition to the compound obtained by the reaction of diamine acid and diisocyanates, a reaction product of urea and aldehydes can be used. Further, a wide range of materials such as polycaprolactone having an ester bond, polystyrene, vinyl chloride and its copolymer, and polyacrylonitrile copolymer can be used.
The vinyl chloride / vinyl acetate copolymer which is a vinyl chloride copolymer preferably has a vinyl chloride component content of 85 to 97% by weight and a degree of polymerization of about 200 to 800. In addition, those containing a vinyl alcohol component, a maleic acid component and the like are also effective.

When polyvinyl aryl carbonate or polyvinyl alkyl carbonate is used in combination with other resin, it is possible to use 1 to 100 parts by weight of other resin to 100 parts by weight of polyvinyl aryl carbonate or polyvinyl alkyl carbonate.

For the purpose of improving the whiteness of the receptive layer to enhance the clarity of the transferred image, imparting writability to the image surface, and preventing retransfer of the transferred image, the sensitization of fluorescence in the receptive layer 3 is increased. Whitening agents and white pigments can be added. Examples of the fluorescent whitening agent include Uvatex O manufactured by Ciba-Gigi Co., Ltd.
Many compounds commercially available as optical brighteners such as B can be used. Examples of the white pigment include titanium oxide, zinc oxide, kaolin, clay, calcium carbonate and fine powder silica, which can be used alone or in combination of two or more kinds. Further, in order to improve the light resistance of the transferred image, one or two additives such as an ultraviolet absorber, a light stabilizer, or an antioxidant are added to the receiving layer.
One or more species can be added if necessary. The amount of the fluorescent whitening agent, white pigment, ultraviolet absorber, light stabilizer, etc. added is 0.05 to 1 with respect to 100 parts by weight of polyvinyl aryl carbonate or polyvinyl alkyl carbonate.
0 parts by weight is suitable, but depending on the purpose, an amount outside the range may be added, and the above-mentioned addition amount is merely an example thereof, and therefore, the addition amount is restricted. is not.

The video printing paper of the present invention may contain a releasing agent in the receiving layer in order to improve the releasing property from the ink ribbon sheet. Examples of the releasing agent include solid waxes such as polyethylene wax, amide wax and Teflon powder, fluorine-based and phosphoric acid ester-based surfactants, silicone oil, and high melting point silicone wax, with silicone oil being preferred. For example, the silicone oil may be oily or reactive (curing) type, and may be used depending on the purpose. Examples of the reaction (curing) type silicone include alcohol-modified silicone oil and isocyanate. Further, as the reaction (curing) type silicone oil, an epoxy-modified silicone oil (epoxy / polyether-modified silicone oil) and a carboxy-modified silicone oil (carboxy / polyether-modified silicone oil) are reaction-cured, or an amino-modified silicone. Those obtained by reaction-curing oil (amino / polyether-modified silicone oil) and carboxy-modified silicone oil (carboxy / polyether-modified silicone oil) are also preferable. The thickness of the release agent layer is preferably 0.01 to 5 μm, but is not particularly limited to this thickness.

An antistatic agent may be contained in the polyvinyl aryl or alkyl carbonate type receiving layer or on the surface of the receiving layer in order to suppress the generation of static electricity during the processing of the video printing paper or during running in the printer.
As the antistatic agent, a surface active agent such as a cationic surface active agent (eg, quaternary ammonium salt, polyamine derivative, etc.), an anionic surface active agent (eg, alkylbenzene sulfonate, alkyl sulfate sodium salt), zwitterionic type Examples thereof include surfactants and nonionic surfactants.

These antistatic agents may be formed by coating on the surface of the receiving layer or added to polyvinyl aryl carbonate or polyvinyl alkyl carbonate.

On the other hand, the dye used in the ink ribbon is optional, but if it is specifically exemplified, the following dyes can be mentioned, for example. (1) Methine dye (A) (Macrolex Yel
low 6G Bayer Co., Ltd. (2) Methine dye (B) (Foron Brilli)
ant Blue SR-PI Sandoz Co., Ltd.) (3) Anthraquinone dye (C) (Macrolex)
Red VioletR Bayer) (4) Azo dye (D) (Sumikaron Red)
(S-BDF manufactured by Sumitomo Chemical Co., Ltd.) (5) Indoaniline dye (E)

For example, a method for synthesizing an indoaniline derivative is as follows. First, 3 g of 2- (n-butyroylamino) -4,6-dichloro-5-methylphenol was dissolved in 200 g of ethanol, and 8 g of sodium carbonate was added thereto.
What was melt | dissolved in 100 g of water was added, and it stirred well. A solution prepared by dissolving 5 g of 4-amino-N (β-hydroxyethyl) -N-ethyl-m-toluidine sulfate in 100 g of water was added thereto and stirred for 30 minutes, and sodium hypochlorite solution 15
g is added little by little, and when the addition is completed, the mixture is stirred for 10 minutes, 300 g of water is added, and filtration is performed to obtain dye crystals.

[0027]

When a polyvinyl aryl carbonate or polyvinyl alkyl carbonate type resin is used as the main component of the receiving layer, the light resistance is improved as compared with the case where a conventionally used polyester or polycarbonate type resin is used. The dyeability is improved by blending a polyvinyl aryl carbonate or polyvinyl alkyl carbonate resin with a compound that enhances the dyeability. Further, the light resistance is further improved by blending the polyvinyl aryl or alkyl carbonate resin with another resin.

[0028]

EXAMPLES Preferred examples of the present invention will be described below based on experimental results.

Synthesis of Resin First, a resin as a material of the receiving layer of the receiving layer sheet was synthesized. Hereinafter, a method for producing polyvinyl phenyl carbonate will be described as a typical example of the method for producing polyvinyl carbonate.

A 500 ml four-necked flask equipped with a stirrer, a temperature system, a dropping funnel, a backflow cooler (equipped with a calcium chloride tube at the top), and a nitrogen gas introduction tube was set on a mantle heater, and polyvinyl alcohol (Japan Synthetic Chemical Industry Co., Ltd., trade name Gohsenol NM-11, viscosity 13-
16, saponification degree 99.0 or more, volatile content 5% or less, ash content 0.7% or less, PH5-7) 8.8 g (stored in a desiccator containing silica gel for 1 week) and pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) , 30 ml of special reagent grade and 250 ml of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) are charged, and the mixture is gently stirred at room temperature for 24 hours while introducing nitrogen gas. Then, 47 g of phenyl chloroformate from the dropping funnel
Is dripped. A white insoluble matter is formed at the same time as the dropping, and the temperature of the content liquid rises. Adjust the dropping rate of chloride to adjust the liquid temperature to 8
Keep below 0 ° C. The whole amount of chloride is added, and after the liquid temperature becomes constant, the mixture is heated, the liquid temperature is set to 100 ° C., and the reaction is performed as it is for 10 hours. During this time, the white precipitate becomes powdery and the liquid turns red. After stopping the heating and allowing the contents to cool to room temperature, the mixture is dripped into 80% methanol water that is vigorously stirred. A white precipitate is formed at the same time as the dropping.
The precipitate is filtered off, washed several times with methanol until chlorine ions are not observed during washing, and dried under reduced pressure (10 mmHg,
50 ° C., 48 hours).

The reaction product is dissolved in methyl ethyl ketone and acetic ester at room temperature and in toluene and cyclohexanone when heated. Methyl ethyl ketone solution (concentration 0.5
(100 g / 100 ml) has an intrinsic viscosity of 1.98, and the infrared absorption spectrum of the film (prepared from a methyl ethyl ketone solution) shows 1770 cm ⁻¹ , 1220 c.
The absorption of the carbonate-bonded carbonyl group near m ⁻¹ ,
The absorption of the monosubstituted aromatic compound is clearly shown around 700 cm ^-1 . Furthermore, the saponification value of carbonate bond (FDS
nell, L .; S. Effre, Encycl, In
d. chem. ANAL, 17, p330 (197)
3), Interscience Publ. The reaction rate of the hydroxyl groups of polyvinyl alcohol obtained from () was 86%. From the above measurement results and raw materials, it is presumed that this reaction product is a polyvinyl phenyl carbonate / vinyl alcohol copolymer in which 86% of the polyvinyl alcohol hydroxyl groups are phenyl carbonate groups and 14% remain unreacted. .. The reaction rate of the polyvinyl alcohol hydroxyl group is preferably 50% or more from the viewpoint of solubility in an organic solvent and physical properties of the film.

Preparation of Receiving Sheet For the receiving sheet, the receiving layer composition was dried on a synthetic paper (produced by Oji Yuka Co., Ltd., trade name FPG-150) having a thickness of 10 μm.
It was prepared by coating so as to have a thickness of m and curing at 50 ° C. for 48 hours. The composition of the receiving layer composition is shown below. Table 1 shows the types of resins and compounds added to each sheet to enhance the dyeing property. Receptor layer composition Resin 20.0 parts by weight Compound for enhancing dyeability 0 to 4 parts by weight Isocyanate 1.0 parts by weight (Takeda Pharmaceutical Co., trade name Takenate D-110N) Modified silicone oil 0.6 parts by weight (Toray Dow Corning, trade name SF8427) Optical brightener 0.04 parts by weight (Ciba Geigy, trade name Ubitex OB) Methyl ethyl ketone 40.0 parts by weight

[0033]

[Table 1]

Ink ribbon Y used : yellow (ribbon VPM-30ST for printing material)
Sony Corporation M: Magenta (Printing material ribbon VPM-30ST)
Sony Corporation C: Cyan (Printing material ribbon VPM-30ST
The method of making the used ink ribbon is as follows. Ink layer composition Dye 3.70 parts by weight Ethyl hydroxyethyl cellulose 7.42 parts by weight (EHEC-LOW Hercules) Toluene 44.44 parts by weight Methyl ethyl ketone 44.44 parts by weight

An ink was prepared by stirring the mixture having the above composition. Then, a dry film thickness of about 1 μm was formed on a 6 μm polyethylene terephthalate (PET) film which was back-treated with a coil bar from the ink layer composition.
To obtain a sublimation transfer sheet, which was used as an ink sheet.

Thermal transfer recording In thermal transfer recording, an ink sheet and a receiving layer sheet are printed on a color video printer (manufactured by Sony Corporation, trade name CVP-G50).
0) was used to carry out 12-step gradation printing.

[0037] 60,000KJ / m ² was irradiated with the light resistance test floor signed image the receiving layer sheet xenon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.). Macbeth reflection densitometer (TR-
924 type), the highest density part and the gradation part near the density of 1.0 were measured, and the residual ratio of the dye was calculated according to the following formula. Residual rate of dye (%) = density after xenon irradiation / density before xenon irradiation × 100

Dark Fading Test Gradation-printed receptor layer sheets were kept in a thermo-hygrostat (Tabay) at 65 ° C. and 85% relative humidity for 10 days, using a Macbeth reflection densitometer (TR-924). The density change before and after the test at the highest density part and around 1.0 was measured, and the residual ratio of the dye was calculated according to the following formula. Residual rate of dye (%) = concentration after test / concentration before test x 1
00

Dyeing Density Measurement Using a Macbeth reflection densitometer (TR-924), the highest density portion of the gradation-printed receiving layer sheet was measured. The measurement results are shown in Tables 2 and 3.

[0040]

[Table 2]

[0041]

[Table 3]

From the test results shown in Tables 2 and 3, the dyeing degree is improved by using the polymer of the present invention as compared with the conventionally used polyester resins (Comparative Examples 1 and 2).
Light resistance, high residual ratio of dye after fading test, light resistance,
It can be seen that durability such as discoloration resistance is improved.

The present invention is not limited to the above-mentioned embodiments, and it goes without saying that various other configurations can be adopted without departing from the gist of the present invention.

[0044]

INDUSTRIAL APPLICABILITY In the present invention, since a polyvinyl aryl or alkyl carbonate type resin is used as the resin of the receiving layer, it is compared with the case of using a polyester type resin generally used as the receiving layer resin. Then, the dyeing property and the light resistance are improved, and the dyeing property and the light resistance can be improved by blending a compound which enhances the dyeing property to the polyvinyl aryl or alkyl carbonate resin. Further, by blending the polyvinyl aryl or alkyl carbonate resin with another resin, there is an advantage that the performance may be further improved.

Claims (3)

[Claims] 1. A video printing paper having a receiving layer to which a dye melted or sublimated by heating is transferred, and an image is formed by the dye transferred to the receiving layer, wherein the receiving layer contains polyvinyl carbonate. Video printing paper characterized by: 2. The video printing paper according to claim 1, wherein the receiving layer contains not more than 50% by weight of another resin compatible with polyvinyl carbonate. 3. The video printing paper according to claim 1, wherein the receiving layer contains a compound for enhancing the dyeing property.