JPH0538882A - Video printing paper - Google Patents

Abstract

PURPOSE:To provide a video printing paper excellent in the light resistance of the image formed by the migration of a dye into its receiving layer. CONSTITUTION:In a video printing paper on which images are formed through dye migration into its receiving layer 3 consisting mainly of resin by heating the dye supported on a base body or dye-containing ink to fuse or sublime the same, the resin in the receiving layer consists mainly of polyvinyl aryl- or alkylurethane.

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 printing paper having a receiving layer mainly composed of polyvinyl aryl or alkyl urethane.

[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.

This video printing paper has a two-layer structure in which a receiving layer is formed on a sheet-shaped substrate. The receiving layer is a layer for receiving (receiving) an image of a dye, for example, a sublimable disperse dye, transferred from the ink ribbon, 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.

[0004]

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.
This is considered to be easily affected by light, humidity, oxygen in the air, etc., because the dye that migrates by the thermal head or the like exists near the surface of the receiving layer. SUMMARY OF THE INVENTION 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 lightfastness and weatherability.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using at least one of polyvinyl aryl urethane or polyvinyl alkyl urethane as a constituent material of the receiving layer, The inventors have found that the light resistance and weather resistance of video printing paper are improved, and have completed the present invention. The video printing paper of the present invention is a video printing paper for forming an image by melting or sublimating a dye or an ink containing the dye supported on a substrate by heating to transfer the dye to a receiving layer mainly made of a resin of the printing paper. In the above, the receiving layer is characterized by containing polyvinyl urethane.

In the video printing paper of the present invention, the receiving layer contains 50% by weight of another resin compatible with polyvinyl urethane.
It is characterized by containing the following. Further, the video printing paper of the present invention is characterized in that the receiving layer contains a compound for enhancing the dyeing property.

The video printing paper 1 of the present invention has a structure having a receiving layer 3 on a sheet-shaped substrate 2 as shown in FIG.

The receiving layer is mainly composed of resin. The present invention is characterized in that polyvinyl urethane is used as the resin forming the receiving layer. This polyvinyl urethane is produced by reacting at least one of aryl isocyanate or alkyl isocyanate with polyvinyl alcohol.

As the above-mentioned aryl isocyanate compound as a raw material, phenyl isocyanate, o-tolyl isocyanate, p-tolyl isocyanate, α-naphthyl isocyanate, β-naphthyl isocyanate, o-
Examples thereof include phenyl phenyl isocyanate, p-phenyl phenyl isocyanate, p-chlorophenyl isocyanate, p-tetra-butyl phenyl isocyanate. Examples of the alkyl isocyanate compound include n
-Butyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate and the like can be mentioned.

The polyvinyl alcohol to be urethanized with these aryl isocyanate compounds or alkyl isocyanate compounds has a saponification degree and a viscosity (degree of polymerization).
Of different, further polyvinyl alcohol derivatives (for example, hydroxyethyl polyvinyl alcohol, hydroxypropyl polyvinyl alcohol, polyvinyl alcohol containing a carboxyl group, etc.), and the like, Gosenol as a commercial product [trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., There are dozens of typical varieties only). However, it is needless to say that the compounds used as the above raw materials are merely representative ones, and the raw materials used in the present invention are not limited thereto.

Further, in the present invention, an additive may be contained together with the above resin in order to increase the dyeing property of the dye and to improve the light resistance and heat resistance. This additive is
It is considered that it is compatible with polyvinyl urethane, promotes the diffusibility of the dye, and has the function of allowing the dye to penetrate into the inside of the receiving layer.

As the above additives, esters, ethers, urethane compounds and the like can be used. The representative compounds are illustrated below, but they are merely examples. Examples of the esters include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate dicyclohexyl phthalate and diphenyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate, dioctyl sepaate and dicyclohexyl azelaate, triphenyl. Phosphates such as phosphate, tricyclohexyl phosphate and triethyl phosphate, isophthalates such as dimethyl phthalate, diethyl isophthalate and dicyclohexyl isophthalate, higher fatty acid esters such as butyl stearate and cyclohexyl laurate, tetraethyl Silicates, silicates such as tetraphenyl silicate, tributylborate, triphenylborate, etc. There is such as acid esters.

As the ethers, diphenyl ether,
Examples of urethane compounds such as dicyclohexyl ether and P-ethoxybenzoic acid methyl ester include n-butylphenyl urethane, m-phenylenedi-n-butylurethane, P-xylenedihexylurethane and diphenylhexamethylenediurethane. Further, there are camphor, low molecular weight polystyrene and the like, phenols such as P phenylphenol and O phenylphenol, and sulfonic acid amides such as N-ethyltoluene sulfonic acid amide.

Further, the receiving layer may be composed of a mixture of polyvinyl urethane and another resin. 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) Those having a urethane bond Polyurethane resin and the like. (C) Polyamide resin having an amide bond. (D) Others Polycaprolactone resin, polystyrene resin, polyvinyl chloride and copolymers thereof, polyacrylonitrile and copolymers thereof.

As the saturated polyester, for example, Byron 200, Byron 290, Byron 600 and the like (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.

Examples of urethane resins include ether type polyurethanes and ester type polyurethanes made from polyether or polyester having a hydroxyl group at the molecular end and isocyanate, and examples of the resin having an amide bond include nylon and other branched groups. There are polyamides derived from diamines and diamines that have carboxylic acids. Furthermore, polycaprolactone and polystyrene with ester bond,
A wide range of materials such as vinyl chloride and its copolymers and polyacrylonitrile copolymers can be used.

When polyvinyl urethane is used in combination with other resin, it is preferable to use 1 to 100 parts by weight of other resin with respect to 100 parts by weight of polyvinyl urethane.

On the other hand, for the purpose of improving the whiteness of the receiving layer to enhance the sharpness of the transferred image, imparting writability to the image surface, and preventing retransfer of the transferred image, Optical brighteners and white pigments can be added.

As the optical brightening agent, many compounds commercially available as the optical brightening agent can be used, for example, Ubitex OB manufactured by Ciba-Gigi Company. As white pigments, titanium oxide, zinc oxide, kaolin,
There are clay, calcium carbonate, fine powder silica and the like, and these 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 may be added to the receptor layer, if necessary. You can These optical brighteners, white pigments,
The amount of ultraviolet absorber, light stabilizer, etc. added is 0.0 with respect to 100 parts by weight of polyvinyl aryl or alkyl urethane.
Although 5 to 10 parts by weight is suitable, 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, high-melting-point silicone wax, and the like. Silicone oil is preferable.

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 0.01
˜5 μm is preferable, but the thickness is not particularly limited.

In order to suppress the generation of static electricity during the process of processing the video printing paper or during running in the printer, polyvinyl aryl or alkyl urethane, and an antistatic agent may be contained in the receiving layer or on the surface of the receiving layer. Antistatic agents include surfactants such as cationic surfactants (eg, quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (eg, alkylbenzene sulfonates, alkyl sulfate sodium salts), zwitterionic surfactants. Activators or nonionic surfactants may be mentioned. These antistatic agents may be formed on the surface of the receiving layer by coating or added to the polyvinyl aryl or alkyl urethane resin.

[0025]

By using polyvinyl urethane as the constituent material of the receiving layer, the dyeing property and the light resistance are improved as compared with the case of using the conventionally used polyester resin or the like. Further, by blending a compound that enhances dyeability with the polyvinyl urethane, dyeability,
Light resistance is improved. Furthermore, the light resistance is further improved by blending the polyvinyl urethane resin with another resin.

[0026]

【Example】

-Specific contents of embodiments- Hereinafter, the specific contents of embodiments of the video printing paper of the present invention will be described. As shown in FIG. 1, the video printing paper 1 of this embodiment has a structure in which a receiving layer 3 is provided on a sheet-like base material 2.

The receiving layer 3 is mainly composed of resin. Here, polyvinyl phenyl urethane was used as this resin. The method for producing this polyvinylphenyl urethane is as follows. First, a 4-necked flask equipped with a stirrer, a backflow cooler (equipped with calcium chloride tube at the tip), a dropping funnel, and a nitrogen gas introduction tube was set in a mantle heater, and dried dimethylformamide [special grade reagent, Japanese reagent Kojunkuyaku Kogyo Co., Ltd., dried by molecular sieve and distilled under reduced pressure] 200 ml, polyvinyl alcohol [Nippon Gosei Kagaku Co., Ltd., trade name GM]
-14 (saponification degree, 86.5 to 89.0 mol%, viscosity,
Heppler viscometer 4%, K solution 20.5 to 24.5)]
8.8 g, dibutyltin dilaurate, and triethylenediamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.04 each
Charge nitrogen and introduce nitrogen gas while stirring (flow rate 10
0 ml / min). Then, 28.6 g of phenylisocyanate [reagent, manufactured by Tokyo Chemical Industry Co., Ltd., distillation (161 to 162 ° C.)] was dropped from the dropping funnel. At this time, heat was generated at the same time as the dropping of the isocyanate, so the dropping rate was adjusted so that the temperature of the contents did not exceed 40 ° C.

Then, after the dripping of the isocyanate was completed and the internal temperature became constant, it was heated for about 1 hour so that the temperature of the contents became 60 ° C. During this time, the initially cloudy content became viscous at the end of the dropwise addition of the isocyanate, and became a transparent viscous liquid when the temperature reached 60 ° C. Then, the reaction was completed by heating at 60 ° C. for 2 hours.
After that, the content liquid was allowed to cool to room temperature and then added dropwise to the vigorously agitated methanol / water (2/8) mixed liquid.
White granules were formed at the same time as the dropping. The fine granular white precipitate was washed several times with methanol / water and then with methanol, and then dried under reduced pressure (10 mmHg, 40 ° C., 48 hours).

The obtained white powdery product was added to dimethylformamide, tetrahydrofuran and dioxane at room temperature,
It was heated and dissolved in ethyl acetate, chloroform, morpholine, cyclohexanone, methyl cellosolve, and a toluene / ethyl alcohol mixture, but was insoluble in methanol, diacetone alcohol, methylene chloride, chlorobenzene, and water. Further, it was found from observation under a microscope with a heating plate that the softening started at around 125 ° C., and the softening started at around 138 ° C.

Tetrahydrofuran solution (concentration 0.250
g / 100 ml) has an intrinsic viscosity of 2.35 (measured at 30 ° C.), and the infrared absorption spectrum of the film (prepared from a tetrahydrofuran solution) shows the presence of urethane groups near 3330 cm ⁻¹ , 1730, 1530 cm.
The absorption near ^-1 appeared strongly, and the absorption of the aromatic nucleus monosubstituted product appeared around 700 cm ^-1 .

The nitrogen content of this white powdery product was measured by elemental analysis to find that it was 6.00%. From this value and the saponification degree of the raw material polyvinyl alcohol (calculated from the catalog value assuming that the saponification degree is 88 mol%), the ratio (%) of polyvinyl alcohol converted to polyvinyl (phenyl) urethane (hereinafter, this value is referred to as the urethane degree) is calculated. When calculated, 67.6% was obtained, and it is estimated that about 2 molecules out of 3 molecules of the polyvinyl alcohol basic molecule are urethane-formed.

From the above experiment and measurement results, it is presumed that the polymer obtained according to this example is a vinyl alcohol / vinyl acetate copolymer containing polyvinylphenyl urethane as a main component. By the production method according to the above, various kinds of polyvinyl urethanes can be produced by selecting various (reaction) raw materials.

The dyes used as the ink layer forming composition in this example are shown below. Methine dye (A) (Macrolex Yellow 6
G, manufactured by Bayer) Methine dye (B) (Freon Brilliant Blue SR-PI, manufactured by Sanddods) Anthraquinone dye (C) (Macrolex Red Violet R, manufactured by Bayer) Azo dye (D ) (Sumikaron Red S-BDF,
Sumitomo Chemical Co., Ltd. Indoaniline dye (E) Yellow (Printing ribbon VPM-30ST, Sony) Magenta (Printing ribbon VPM-30ST, Sony) Cyan (Printing ribbon VPM-30ST, Sony (manufactured by Sony) Yellow (printing material ribbon UPC-3010, manufactured by Sony Corporation) Magenta (printing material ribbon UPC-3010, manufactured by Sony Corporation) Cyan (printing material ribbon UPC-3010, manufactured by Sony Corporation) Indoaniline The structural formula of the system dye (E) is as shown in Chemical formula 1.

[0034]

[Chemical 1]

The method of synthesizing this dye is as follows. First, in order to synthesize an indoaniline derivative, 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 dissolved therein in 100 g of water. Add and stir well. There, 4-amino-N (β
-Hydroxyethyl) -N-ethyl-m toluidine sulfate (5 g) dissolved in 100 g of water was added and stirred for 30 minutes,
15 g of sodium hypochlorite solution was added little by little, and when the addition was completed, the mixture was stirred for 10 minutes, 300 g of water was added, and filtration was performed to obtain dye crystals. The reaction formula is shown below.

[0036]

[Chemical 2]

Next, 2 g of the resulting dye crystals were 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. The reaction formula is shown below.

[0038]

[Chemical 3]

Then, the obtained compound was purified by subjecting it to column chromatography (filler: Wako Pure Chemical Industries, Ltd., trade name Wakogel C-200) using chloroform as a developing solvent, and used as Dye 1.

Then, an ink layer composition containing the above dyes was prepared according to the following composition. Ink layer composition Dye (dye of) 3.70 parts by weight Ethyl hydroxyethyl cellulose 7.42 parts by weight (EHEC-LOW Hercules Co., Ltd.) 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, this ink layer composition was applied onto a 6 μm polyethylene terephthalate (PET) film back-treated using a coil bar so that the dry film thickness was about 1 μm to prepare a sublimation type transfer sheet, which was used as an ink sheet.

Using each of the ink sheets produced as described above, thermal transfer recording was carried out on a receiving layer sheet which was a transfer medium.

The receptor layer sheet was prepared by coating the receptor layer composition on 150 μm synthetic paper (trade name: FPG-150 manufactured by Oji Yuka Co., Ltd.) so that the dry film thickness was 10 μm.
It is prepared by curing at 48 ° C. for 48 hours. The composition of the receiving layer composition is as shown below.

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 Fubitex OB) Methyl ethyl ketone 40.0 parts by weight

[0045]

[Table 1]

As the thermal transfer recording, 12 steps of stairstep printing was performed on the ink sheet and the receiving layer sheet using a color video printer (manufactured by Sony Corporation, trade name CVP-G500).

In order to perform a light resistance test, the gradation-printed receptor layer sheet was irradiated with a xenon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) at 60,000 KJ / m ² , and the density before and after irradiation was measured by a Macbeth reflection densitometer ( TR-924 type)
Was used to measure the highest density part and the gradation part near the density of 1.0, and the residual ratio of the dye was calculated according to the following formula (4).

[0048]

[Equation 1]

Then, in order to perform a dark fading test, the gradation-printed receiving layer sheet was placed in a thermo-hygrostat (made by Tabai) for 6 minutes.
It was stored at 5 ° C., 85% RH for 10 days, and using a Macbeth reflection densitometer (TR-924), the density change before and after the test at the highest density part and near the density of 1.0 was measured. It was calculated according to the equation (5).

[0050]

[Equation 2]

Further, in order to measure the dyeing density, the maximum density part of the gradation printed receptor layer sheet was measured using a Macbeth reflection densitometer (TR-924). Tables 2 and 3 collectively show the results of dyeing density, light fastness test, and dark fading test of printed images using the polymer of the present invention as a receiving layer.

[0052]

[Table 2]

[0053]

[Table 3]

From the test results of Tables 2 and 3, the use of the polymer of the present invention improves the dyeing degree, the light fastness, and the light resistance of the polyester resins (Comparative Examples 1 and 2) used conventionally. It can be seen that the residual ratio of the dye after the fading test is high and the durability such as light resistance and fading 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]

EFFECTS OF THE INVENTION According to the present invention, the composition of the receiving layer is made of a polyvinyl aryl or alkyl urethane resin so that the dyeing property can be improved as compared with the case where a conventionally used polyester resin or the like is used. The dye fastness and the light fastness can be improved by blending the polyvinyl aryl or alkyl urethane resin with a compound that enhances the dye fastness. Further, by blending the polyvinyl aryl or alkyl resin with another resin, the dyeing property and the light resistance can be further improved in some cases.

[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] October 7, 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 printing paper having a receiving layer mainly composed of polyvinyl aryl or alkyl urethane.

[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.

This video printing paper has a two-layer structure in which a receiving layer is formed on a sheet-shaped substrate. The receiving layer is a layer for receiving (receiving) an image of a dye, for example, a sublimable disperse dye, transferred from the ink ribbon, 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.

[0004]

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. SUMMARY OF THE INVENTION 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 lightfastness and weatherability.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using at least one of polyvinyl aryl urethane or polyvinyl alkyl urethane as a constituent material of the receiving layer, The inventors have found that the light resistance and weather resistance of video printing paper are improved, and have completed the present invention. The video printing paper of the present invention is a video printing paper for forming an image by melting or sublimating a dye or an ink containing the dye supported on a substrate by heating to transfer the dye to a receiving layer mainly made of a resin of the printing paper. In the above, the receiving layer is characterized by containing polyvinyl urethane. Further, the video printing paper of the present invention is characterized in that the receiving layer contains 50% by weight or less of another resin compatible with polyvinyl urethane. Further, the video printing paper of the present invention is characterized in that the receiving layer contains a compound for enhancing the dyeing property.

As shown in FIG. 1, the video printing paper 1 of the present invention has a structure having a receiving layer 3 on a sheet-shaped substrate 2.

The receiving layer is mainly composed of resin. The present invention is characterized in that polyvinyl urethane is used as the resin forming the receiving layer. This polyvinyl urethane is produced by reacting at least one of aryl isocyanate or alkyl isocyanate with polyvinyl alcohol.

As the above-mentioned aryl isocyanate compound as a raw material, phenyl isocyanate, o-tolyl isocyanate, p-tolyl isocyanate, α-naphthyl isocyanate, β-naphthyl isocyanate, o-
Examples thereof include phenyl phenyl isocyanate, p-phenyl phenyl isocyanate, p-chlorophenyl isocyanate, p-tetra-butyl phenyl isocyanate. Examples of the alkyl isocyanate compound include n
-Butyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate and the like can be mentioned.

The polyvinyl alcohol to be urethanized with these aryl isocyanate compounds or alkyl isocyanate compounds has a saponification degree and a viscosity (degree of polymerization).
Of different, further polyvinyl alcohol derivatives (for example, hydroxyethyl polyvinyl alcohol, hydroxypropyl polyvinyl alcohol, polyvinyl alcohol containing a carboxyl group, etc.), and the like, Gosenol as a commercial product [trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., There are dozens of typical varieties only). However, it is needless to say that the above-mentioned raw materials are merely representative compounds, and the raw materials used in the present invention are not limited thereto.

Further, in the present invention, an additive may be contained together with the above resin in order to increase the dyeing property of the dye and improve the light resistance and heat resistance. This additive is
It is considered that it is compatible with polyvinyl urethane, promotes the diffusibility of the dye, and has the function of allowing the dye to penetrate into the inside of the receiving layer.

As the above additives, esters, ethers, urethane compounds and the like can be used. The representative compounds are illustrated below, but they are merely examples. Examples of the esters include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate dicyclohexyl phthalate and diphenyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate, dioctyl sepaate and dicyclohexyl azelaate, triphenyl. Phosphates such as phosphate, tricyclohexyl phosphate and triethyl phosphate, isophthalates such as dimethyl phthalate, diethyl isophthalate and dicyclohexyl isophthalate, higher fatty acid esters such as butyl stearate and cyclohexyl laurate, tetraethyl Silicates, silicates such as tetraphenyl silicate, tributylborate, triphenylborate, etc. There is such as acid esters.

As the ethers, diphenyl ether,
Examples of urethane compounds such as dicyclohexyl ether and P-ethoxybenzoic acid methyl ester include n-butylphenyl urethane, m-phenylenedi-n-butylurethane, P-xylenedihexylurethane and diphenylhexamethylenediurethane. Further, there are camphor, low molecular weight polystyrene and the like, phenols such as P phenylphenol and O phenylphenol, and sulfonic acid amides such as N-ethyltoluene sulfonic acid amide.

Further, the receiving layer can be composed of a mixture of polyvinyl urethane and another resin. 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) Those having a urethane bond Polyurethane resin and the like. (C) Polyamide resin having an amide bond. (D) Others Polycaprolactone resin, polystyrene resin, polyvinyl chloride and copolymers thereof, polyacrylonitrile and copolymers thereof.

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.

Examples of urethane resins include ether type polyurethanes and ester type polyurethanes made of polyether or polyester having a hydroxyl group at the molecular end and isocyanate, and examples of the resin having an amide bond include nylon and other branched groups. There are polyamides derived from diamines and diamines that have carboxylic acids. Furthermore, polycaprolactone and polystyrene with ester bond,
A wide range of materials such as vinyl chloride and its copolymers and polyacrylonitrile copolymers can be used.

When polyvinyl urethane is used in combination with another resin, it is preferable to use 1 to 100 parts by weight of the other resin with respect to 100 parts by weight of the polyvinyl urethane.

For the purpose of improving the whiteness of the receiving layer to improve the sharpness of the transferred image, imparting writability to the image surface, and preventing retransfer of the transferred image, the above-mentioned receiving layer is increased in fluorescence. Whitening agents and white pigments can be added.

As the fluorescent whitening agent, many compounds commercially available as a fluorescent whitening agent such as Ubitex OB manufactured by Ciba-Geigi can be used. As white pigments, titanium oxide, zinc oxide, kaolin,
There are clay, calcium carbonate, fine powder silica and the like, and these 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 may be added to the receiving layer, if necessary. You can These optical brighteners, white pigments,
The amount of ultraviolet absorber, light stabilizer, etc. added is 0.0 with respect to 100 parts by weight of polyvinyl aryl or alkyl urethane.
Although 5 to 10 parts by weight is suitable, 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, high-melting-point silicone wax, and the like. Silicone oil is preferable.

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 0.01
˜5 μm is preferable, but the thickness is not particularly limited.

In order to suppress generation of static electricity during the process of processing the video printing paper or during running in the printer, polyvinyl aryl or alkyl urethane, and an antistatic agent may be contained in the receiving layer or on the surface of the receiving layer. Antistatic agents include surfactants such as cationic surfactants (eg, quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (eg, alkylbenzene sulfonate, sodium alkylsulfate ester salts), zwitterionic surfactants. Activators or nonionic surfactants may be mentioned. These antistatic agents may be formed on the surface of the receiving layer by coating or added to the polyvinyl aryl or alkyl urethane resin.

On the other hand, the dye used in the ink ribbon is arbitrary, but if it is specifically exemplified, for example, the following dyes can be mentioned. Methine dye (A) (Macrolex Yellow 6
G, manufactured by Buyer) methine dye (B) (Freon Brilliant Blue SR-PI, manufactured by Sanddods) Anthraquinone dye (C) (Macrolex Red Violet R, manufactured by Bayer) Azo dye (D ) (Sumikaron Red S-BDF,
Sumitomo Chemical Co., Ltd.) Indoaniline dye (E) For example, the method for synthesizing an indoaniline derivative is as follows. First, 2- (n-butyroylamino)-
3 g of 4,6-dichloro-5-methylphenol was dissolved in 200 g of ethanol, and 8 g of sodium carbonate was added thereto.
Add what was dissolved in 00g and stir well. To there 4
-Amino-N (β-hydroxyethyl) -N-ethyl-
m Toluidine sulfate (5 g) dissolved in 100 g of water was added and stirred for 30 minutes, 15 g of sodium hypochlorite solution was added little by little, and when the addition was completed, the mixture was stirred for 10 minutes, and water 3
Add 00 g and filter to obtain dye crystals.

[0025]

By using polyvinyl urethane as the constituent material of the receiving layer, the dyeing property and the light resistance are improved as compared with the case of using the conventionally used polyester resin or the like. Further, by blending a compound that enhances dyeability with the polyvinyl urethane, dyeability,
Light resistance is improved. Furthermore, the light resistance is further improved by blending the polyvinyl urethane resin with another resin.

[0026]

EXAMPLES The concrete contents of the examples of the video printing paper of the present invention will be described below. As shown in FIG. 1, the video printing paper 1 of this embodiment has a structure in which a receiving layer 3 is provided on a sheet-like base material 2.

The receiving layer 3 is mainly composed of resin. Here, polyvinyl phenyl urethane was used as this resin. Synthesis of Polyvinyl Urethane The method for producing polyvinyl phenyl urethane is as follows. First, set a 4-necked flask equipped with a stirrer, a backflow cooler (equipped with calcium chloride tube at the tip), a dropping funnel, and a nitrogen gas introduction tube in the mantle heater,
Dry dimethylformamide [special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd., dried with molecular sieve and distilled under reduced pressure] 200 ml, polyvinyl alcohol [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name GM-14 (saponification degree, 8
6.5-89.0 mol%, viscosity, Heppler viscometer 4%,
K solution 20.5 to 24.5)] 8.8 g and 0.04 g of each of dibutyltin dilaurate and triethylenediamine (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were introduced, and nitrogen gas was introduced while stirring (flow rate 100 ml / min). did. Then, from the dropping funnel, phenylisocyanate [reagent, manufactured by Tokyo Chemical Industry Co., Ltd., distillation (161 to 162 ° C.)] 2
8.6 g was added dropwise. At this time, heat was generated at the same time as the dropping of the isocyanate, so the dropping rate was adjusted so that the temperature of the contents did not exceed 40 ° C.

Then, after the dripping of the isocyanate was completed and the internal temperature became constant, it was heated for about 1 hour so that the temperature of the contents became 60 ° C. During this time, the initially cloudy content became viscous at the end of the dropwise addition of the isocyanate, and became a transparent viscous liquid when the temperature reached 60 ° C. Then, the reaction was completed by heating at 60 ° C. for 2 hours.
After that, the content liquid was allowed to cool to room temperature and then added dropwise to the vigorously agitated methanol / water (2/8) mixed liquid.
White granules were formed at the same time as the dropping. The fine granular white precipitate was washed several times with methanol / water and then with methanol, and then dried under reduced pressure (10 mmHg, 40 ° C., 48 hours).

The obtained white powdery product was added to dimethylformamide, tetrahydrofuran and dioxane at room temperature,
It was heated and dissolved in ethyl acetate, chloroform, morpholine, cyclohexanone, methyl cellosolve, and a toluene / ethyl alcohol mixture, but was insoluble in methanol, diacetone alcohol, methylene chloride, chlorobenzene, and water. Further, it was found from observation under a microscope with a heating plate that the softening started at around 125 ° C., and the softening started at around 138 ° C.

Tetrahydrofuran solution (concentration 0.250
g / 100 ml) has an intrinsic viscosity of 2.35 (measured at 30 ° C.), and the infrared absorption spectrum of the film (prepared from a tetrahydrofuran solution) shows the presence of urethane groups near 3330 cm ⁻¹ , 1730, 1530 cm.
The absorption near ^-1 appeared strongly, and the absorption of the aromatic nucleus monosubstituted product appeared around 700 cm ^-1 .

The nitrogen content of this white powdery product was measured by elemental analysis to find that it was 6.00%. From this value and the saponification degree of the raw material polyvinyl alcohol (calculated from the catalog value assuming that the saponification degree is 88 mol%), the ratio (%) of polyvinyl alcohol converted to polyvinyl (phenyl) urethane (hereinafter, this value is referred to as the urethane degree) is calculated. When calculated, 67.6% was obtained, and it is estimated that about 2 molecules out of 3 molecules of the polyvinyl alcohol basic molecule are urethane-formed.

From the above experiment and measurement results, it is presumed that the polymer obtained according to this example is a vinyl alcohol / vinyl acetate copolymer containing polyvinylphenyl urethane as a main component. By the production method according to the above, various kinds of polyvinyl urethanes can be produced by selecting various (reaction) raw materials.

Preparation of Receptor Layer Sheet The receptor layer sheet was prepared by mixing the 150 μm synthetic paper (Oji Yuka Co., Ltd., trade name FPG-150) with the receptor layer composition to give a dry film thickness of 10
It is prepared by coating so as to have a thickness of μm and curing at 50 ° C. for 48 hours. The composition of the receiving layer composition is as shown below. Table 1 shows the types and amounts of the polyvinyl urethane used in each sheet and the ester compound added to enhance the dyeing property.
Shown in.

Receptor layer composition Resin 20.0 parts by weight (see Table 1) Compound for improving dyeability 0-4 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 Fubitex OB) Methyl ethyl ketone 40.0 parts by weight

[0035]

[Table 1]

Ink ribbon Y used : yellow (ribbon VPM-30ST for printing material,
Sony: M: Magenta (Printing material ribbon VPM-30ST,
Sony: C: Cyan (printing material ribbon VPM-30ST, Sony)

The method of producing 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 composition in the above ratio. Then, this ink layer composition was applied onto a 6 μm polyethylene terephthalate (PET) film back-treated using a coil bar so that the dry film thickness was about 1 μm to prepare a sublimation type transfer sheet, which was used as an ink sheet.

Thermal transfer recording For thermal transfer recording, an ink sheet and a receiving layer sheet are color video printers (manufactured by Sony Corporation, trade name CVP-G).
500) was used to perform 12-step gradation printing.

The light resistance test floor signed image the receiving layer sheet 60,000KJ / m ² was irradiated with xenon arc fade meter (manufactured by Suga Test Instruments), Macbeth reflection densitometer density before and after irradiation (TR-92
4 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 (4).

[0041]

[Equation 1]

Dark Fading Test Gradation-printed receptor layer sheets were stored in a thermo-hygrostat (Tabay) at 65 ° C. and 85% RH for 10 days, and then 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 (5).

[0043]

[Equation 2]

Measurement of Dyeing Density 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.

[0045]

[Table 2]

[0046]

[Table 3]

From the test results shown in Tables 2 and 3, in comparison with the conventionally used polyester resins (Comparative Examples 1 and 2), when polyvinyl urethane was used, the dyeing degree was improved, and the light fastness and fading resistance tests were conducted. It can be seen that the residual ratio of the dye afterward is high and the durability such as light resistance and fading resistance is improved.

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

[0049]

EFFECTS OF THE INVENTION According to the present invention, the composition of the receiving layer is made of a polyvinyl aryl or alkyl urethane resin so that the dyeing property can be improved as compared with the case where a conventionally used polyester resin is used. Further, the light resistance is improved, and the dyeability and the light resistance can be improved by compounding the polyvinyl aryl or alkyl urethane resin with a compound that enhances the dyeing property. Further, by blending the polyvinyl aryl or alkyl resin with another resin, the dyeing property and the light resistance can be further improved in some cases.

Claims (3)

[Claims] 1. A video printing paper for forming an image by melting or sublimating a dye or an ink containing the dye supported on a substrate by heating to transfer the dye to a receiving layer mainly composed of a resin of the printing paper to form an image. Video printing paper, characterized in that the layer contains polyvinyl urethane. 2. The video printing paper according to claim 1, wherein the receiving layer contains 50% by weight or less of another resin compatible with polyvinyl urethane. 3. The video printing paper according to claim 1, wherein the receiving layer contains a compound for enhancing the dyeing property.