JPH0911644A - Printing paper and image forming method using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] To increase the saturation of an image formed on photographic paper and to improve the fixing property of the formed image. [Structure] In a photographic paper comprising a support and a dye-receiving layer formed thereon, the dye-receiving layer has the following (I) or (I
I) (I) ion-exchange the interlayer ions of the swellable layered silicate with ions that are ion-exchangeable with the cationic dye, and then acid-treat the acid-treated clay-organic composite (II) swellable layered silicate, Next, it contains a clay-organic composite in which the interlayer ions of the acid-treated swelling layered silicate are ion-exchanged with a cationic dye for ion exchangeable ions, and a polymer binder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic printing paper used for forming a dye image on photographic printing paper by a thermal transfer system and an image forming method using the photographic printing paper.

[0002]

2. Description of the Related Art Recently, in order to print out an image photographed by an electronic still camera or the like on a photographic printing paper like a silver halide photograph, an image formation by a sublimation thermal transfer system has been attempted.

In this sublimation type thermal transfer system, an ink ribbon containing a dye is brought into contact with a photographic printing paper on which a dye receiving layer is formed, and the ink ribbon is heated by a thermal head or the like.
The dye of the ink ribbon is transferred to the dye receiving layer of the printing paper by sublimation or thermal diffusion. Here, a resin such as polyester is used as the dye receiving layer of the printing paper, and a disperse dye is used as the dye of the ink ribbon.

By the way, the dispersive paints which are usually used in this type of system are variously devised as disclosed in JP-A-1-269989 and JP-A-1-275096. However, this dispersive paint is retained in the dye receiving layer by interacting with the binder polymer of the dye receiving layer, such as van der Waals force, inter-dipole force, hydrogen bond, etc., after moving to the dye receiving layer. It is just being done. Therefore, after the image is formed, when a resin or solvent having a higher affinity for the dye forming the image comes into contact with the image, or the above-described interaction is canceled in the dye receiving layer forming the image. When the heat energy is supplied, the migration or elution of the dye is induced, which causes a problem such as blurring of the image.

Under these circumstances, for example, Japanese Patent Laid-Open No. 59-59
78893, JP 60-2398, JP 60-110494, and JP 60-22078.
No. 5, JP-A-60-260381, etc., a method of fixing an image by forming a chemical bond has also been proposed.

The methods disclosed therein are methods in which a dye having a group capable of reacting with an epoxy group or an isocyanate group is used, and the compound having the epoxy group or the isocyanate group is contained in the dye receiving layer. It is a method of using a dye having a group or a methacryloyl group and containing a compound having active hydrogen in the dye receiving layer,
Furthermore, a method of using a dye capable of forming a metal complex and containing a metal compound in the dye receiving layer, a low molecular compound having an active methyl group (or a methylene group) is sublimated and transferred to form an aldehyde (nitroso) in the dye receiving layer. For example, a method of reacting with a compound to form a dye.

However, in the method based on the formation of chemical bonds, the reactivity of the dye and the dye receiving layer is too high and the storage stability is poor, and the reaction is not completed in a short time, so that it takes a long time to form a stable image. However, there are drawbacks such as difficulty in preparing dyes and limited types of dyes that can be used.
Furthermore, it is hard to say that the fixing property is sufficient even by these methods.

A method for fixing an image is disclosed in Japanese Patent Laid-Open No.
-299183, JP-A-6-24163, etc., a compound (clay organic complex) in which an exchangeable cation between layers of a clay mineral is replaced with a quaternary ammonium ion, a phosphonium ion or the like. There has been proposed a method of image-wise transferring a cationic dye to the.

[0009]

However, it has been desired to further improve the image fixing property on photographic paper even with the above-mentioned method utilizing clay minerals. It has also been desired to further enhance the saturation of an image so that a high quality image can be formed.

The present invention is intended to solve the problems of the prior art and has an excellent thermal transfer sensitivity, a fixing property comparable to that of a silver salt photographic image, and a high saturation. It is an object of the present invention to provide a photographic printing paper capable of obtaining a high-quality image having a color and an image forming method using the photographic printing paper.

[0011]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that as a clay organic composite, a swellable layered silicate is converted into a clay organic composite by ion exchange. After that, the clay-organic composite is prepared by subjecting the swellable layered silicate that has been acid-treated or pre-acid-treated to ion exchange to contain this clay-organic composite in the dye receiving layer of photographic paper. When a cationic dye is transferred to the dye receiving layer to form a dye image, the cation portion of the dye and the anion portion of the clay organic complex form an ionic bond, and the dye image is converted into an insoluble and infusible state. It was found that it will be firmly established. The present invention has been completed based on such findings.

That is, the present invention provides a photographic printing paper comprising a support and a dye-receiving layer formed thereon, wherein the dye-receiving layer has the following (I) or (II) (I) swellable layered silicate. Of the clay-organic composite (II) swellable layered silicate acid-exchanged with an ion exchangeable ion with a cationic dye, and then acid-treated, and then acid-treated swellable layered silicate Disclosed is a photographic printing paper comprising a clay-organic composite in which interlayer ions are ion-exchanged with a cationic dye, and a polymer binder.

An image forming method is characterized in that an ink ribbon containing a cationic dye is brought into contact with the photographic paper of the present invention, and the cationic dye is transferred from the ink ribbon to the photographic paper by heat to fix the photographic dye. I will provide a.

Hereinafter, the present invention will be described in detail.

The photographic printing paper of the present invention has a dye-receptive layer in which a specific clay-organic complex, that is, (I) the interlayer ions of the swellable layered silicate are ion-exchanged with a cationic dye to form an ion-exchangeable ion. Then, the acid-treated clay organic composite or (II) the swellable layered silicate was acid-treated, and then the interlayer ion of the acid-treated swellable layered silicate was ion-exchanged with a cationic dye It is characterized by containing a clay organic composite.

When added to water, the swelling layered silicate used for forming the clay organic composites (I) and (II) takes in water between layers and swells to form a sol or gel, and also a positive It is a silicate that has a unique property of having ion exchange ability. Examples of such swelling layered silicates include smectite and swelling mica. Here, as the smectite, natural products or chemical compounds such as hectorite, saponite, stevensite, beidellite, montmorillonite, nontronite, their substitution products, derivatives or mixtures thereof can be used. Furthermore, natural or synthetic vermiculite, fluorine vermiculite and the like can also be used. The swelling mica is a natural or synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine-mica having a lithium ion or Na ion between layers, a substitution product thereof, Derivatives or mixtures thereof can be used.

As the swellable layered silicate, either a natural product or a synthetic product can be used as described above, but a natural swellable layered silicate is used because the content of impurities is small. Purified products and synthetic products are preferred.

Among the compounds, synthetic smectites are preferable, and in particular, the formula (1)

[0019]

_{Embedded image} X _{0.1 to 1.0} Mg _{2.4 to 2.9} Li _{0.1 to 0.6} Si _{3.5 to 4.5} O _{9.5 to 10.5} (OH and / or F) _{1.5 to 2.5} (1) (wherein X is an interlayer ion, Synthetic smectites representing Li ions and / or Na ions) are preferred. The synthetic smectite of the formula (1) can be obtained as a pure white powder. The clay-organic composite obtained by substituting the interlayer ions of this synthetic smectite with ions capable of ion-exchange with the cationic dye is also visually transparent without absorption in the visible region. Then, this clay organic composite forms a dye receiving layer from this and a binder polymer having a refractive index close to it, and a cationic dye is transferred to this dye receiving layer to obtain a dye image with high saturation and high quality. It is possible.

The synthetic smectite of the formula (1) is, for example,
It can be synthesized according to the method described in JP-B-61-12848. That is, a homogeneous mixture of silicic acid and magnesium salt is reacted with an alkaline solution to synthesize a silicon-magnesium complex, the by-produced electrolyte is removed, and the obtained silicon-magnesium complex is charged with lithium ions and if necessary. Sodium ion and / or fluorine ion, and hydrothermally react at 100 to 350 ° C.,
Then, it can be obtained by drying.

In this case, the hydrothermal reaction temperature is 180 to 300.
C., and the hydrothermal reaction time is preferably 8 hours or longer. Thereby, the ion exchange ability between the cationic dye and the ion capable of ion exchange can be improved. When the hydrothermal reaction temperature is lower than 180 ° C, the ion exchange capacity of the obtained synthetic smectite is lowered. On the contrary, if the hydrothermal reaction temperature is higher than 300 ° C., the reaction operation becomes difficult.

A small amount of impurities may be contained in the structure of the synthetic smectite of the formula (1) or between layers. Therefore, the synthetic smectite containing such impurities is also included in the synthetic smectite of the formula (1).

As the synthetic smectite of the formula (1), commercially available ones can be used, and for example, Lucentite: SW manufactured by Coop Chemical Co., Ltd. can be used.

In addition to this, as the swellable layered silicate used in the present invention, a commercially available product can be used. For example, Somasif (clay mineral name: swellable mica, manufactured by Coop Chemical Co., Ltd.) , Smecton (clay mineral name: saponite,
Kunimine Industry Co., Ltd.), veegum (clay mineral name: natural hectorite, (US) Binder Built Co., Ltd.), Kunipia (clay mineral name: montmorillonite, Kunimine Industry Co., Ltd.), Laponite (clay mineral name: Hect) Light,
Raporte Co., Ltd. etc. can be used.

In the photographic printing paper of the present invention, the swellable layered silicate as described above is used as a clay organic complex by the method (I) or (II) and used. That is, as the clay-organic composite used in the present invention, (I) the interlayer ion of the swellable layered silicate is ion-exchanged with a cationic dye for an ion-exchangeable ion, and then a clay organic compound obtained by acid treatment is obtained. It is obtained by first acid-treating the complex or (II) swellable layered silicate, and then ion-exchanged the interlayer ion of the acid-treated swellable layered silicate with an ion exchangeable ion with a cationic dye. Clay organic composites are used.

In any of the methods (I) and (II), an ion that is ion-exchanged with the interlayer ion X of the swellable layered silicate and is ion-exchangeable with the cationic dye is an organic positive ion. I can give you ions.

When the interlayer cations of the swellable layered silicate are ion-exchanged with organic cations, the interlayer distance of the swellable layered silicate is expanded, and the hydrophobic chains of the organic cations are inherently hydrophilic. The swellable layered silicate becomes hydrophobic and becomes easily compatible with various organic compounds, especially a polymer binder and its organic solvent. Therefore, by exchanging the interlayer ions of the swellable layered silicate with an organic cation, the swellable layered silicate can be provided with a function capable of ion-exchange of a cationic dye, and at the same time, the coating performance as a dye receiving layer is also improved. It is possible to improve.

Suitable examples of such organic cations include quaternary ammonium ions and phosphonium ions.

In the case of the quaternary ammonium ion, those having an alkyl group are preferable, and those having an alkyl group having 4 or more carbon atoms, particularly 8 or more carbon atoms are preferable. this is,
This is because if the alkyl group has a small number of carbon atoms, a sufficient interlayer distance cannot be secured, and the ion exchange capacity for the dye may be insufficient. As such a quaternary ammonium ion, more specifically, tetra-n-
Examples thereof include decyl ammonium ion and tetra-n-dodecyl ammonium ion.

Among the organic cations, the phosphonium ion is, for example, an alkylphosphonium ion,
An aryl phosphonium ion etc. can be mentioned.

As a method of ion-exchanging such an organic cation with the interlayer ion X of the swelling layered silicate before or after the acid treatment to obtain a clay organic composite, for example, before the acid treatment. Alternatively, for any swellable layered silicate after acid treatment, the swellable layered silicate is dispersed in water to form a suspension, and an organic cation is mixed therein with stirring to obtain a product obtained. Can be separated and dried.

In any of the above methods (I) and (II), the acid used for the acid treatment of the swellable layered silicate is not particularly limited, and examples thereof include minerals such as sulfuric acid, hydrochloric acid and nitric acid. Acids and organic acids such as citric acid and acetic acid can be used. And as a method of treating the swellable layered silicate with these acids, in any of the above methods (I) or (II), after the ion exchange or before the ion exchange swellable layered silicate It may be dispersed in water, and the acid may be added to the dispersion in an amount such that the dispersion becomes weakly basic to acidic. By performing the acid treatment in this manner, the ion exchange ability of the swellable layered silicate with respect to the cationic dye can be improved, and thus the fixability of the image formed on the photographic paper can be improved. The reason why the ion-exchange ability of the swellable layered silicate with respect to the cationic dye is improved by the acid treatment is considered to be that impurities between the layers of the swellable layered silicate are removed by the acid treatment.

On the other hand, as the polymer binder used in the dye receiving layer of the photographic printing paper of the present invention, a thermoplastic resin which has been widely and commonly used in the dye receiving layer of photographic printing paper in the thermal transfer system has been used. be able to. However, those containing a substituent that inhibits the fixing action of the dye, for example, an ammonium group that is relatively more ion-exchanged between the layers of the clay organic composite than the cationic dye are not preferable. Further, as the polymer binder, in order to enhance the saturation of the dye image formed in the dye receiving layer, one having a refractive index similar to that of the swellable layered silicate or clay organic complex is used. More preferably. Therefore, as the thermoplastic resin suitable for the polymer binder in the present invention, for example, polyvinyl butyral resin,
Polyvinyl acetal resin, polyester resin, polyacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin, cellulose ester resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene-anhydrous Maleic acid resin, polyvinyl chloride resin, polyacrylonitrile resin and the like can be used.

In the dye receiving layer, the clay organic composite and the polymer binder are preferably blended in such an amount that the clay organic composite is 5 to 90% by weight of the solid component constituting the dye receiving layer. . If the amount of the clay organic complex is less than 5% by weight, the fixing effect of the dye image cannot be sufficiently enhanced, and if it exceeds 90% by weight, the dye receiving layer cannot be formed into a flexible and good film.

A plasticizer may be added to the dye-receptive layer in order to control the glass transition point Tg of the polymer binder, as long as it does not impair the fixability of the dye, and various auxiliary additives may be added. Is also good.

As the support constituting the photographic printing paper of the present invention, a support conventionally used can be used. For example, paper, synthetic paper, plastic film, metal plate, metal foil, plastic film deposited with metal such as aluminum, and the like can be used.

The photographic printing paper of the present invention comprises a dye-receiving layer in which a clay organic composite and a polymer binder are mixed and dispersed with a solvent, if necessary, and the clay organic composite is swollen with the polymer binder. It can be produced by preparing a coating composition for forming, coating this on a support and forming a film to form a dye receiving layer.

The photographic paper of the present invention can be used for various image forming methods using various inks.
A thermal transfer recording method using a cationic dye, that is, a method of forming an image by bringing an ink ribbon containing a cationic dye into contact with a printing paper and transferring the cationic dye from the ink ribbon to the printing paper by thermal stimulation to fix the ink. In contrast, it can be preferably used. This makes it possible to form a highly saturated image with good fixability. this is,
This is because the cation portion of the cationic dye exchanges ions with the organic cations that are ionically bonded between the layers of the synthetic smectite to form an ionic bond, thereby fixing the image. Therefore, the present invention also includes a method of forming an image on the printing paper of the present invention by a thermal transfer recording method using such a cationic dye.

Here, as the cationic dye, a water-soluble dye having an amine salt or a quaternary ammonium group, for example, an azo dye, a triphenylmethane dye, an azone dye,
Examples thereof include oxazine dyes and thiazine dyes. More specifically, C.I. I Basic Yellow 1,2,11,13,14,19,21,25,2
8, 32, 33, 34, 35, 36 (yellow type),
C. I Basic Red 1,2,9,12,13,1
4,15,17,18,22,23,24,27,2
9, 32, 38, 39, 40, C.I. I Basic Vio Red 7,10,15,21,25,26,27,28
(Magenta type), C.I. I Basic Blue 1, 3, 5,
7, 9, 19, 21, 22, 24, 25, 26, 28,
29, 40, 41, 44, 45, 47, 54, 58, 5
9, 60, 64, 65, 66, 67, 68, 75 (cyan system), C.I. I basic black 2,8 (black type) and the like can be mentioned.

Such cationic dyes are usually water-soluble. On the other hand, the polymer binder that constitutes the dye receiving layer of the photographic paper together with the above-mentioned clay organic composite is hydrophobic.
Therefore, in the present invention, the dye is preferably subjected to a hydrophobizing treatment in order to rapidly transfer the dye to the clay-organic complex swollen in the hydrophobic polymer binder. For example, it is preferable to make a hydrophilic cationic dye hydrophobic by substituting its counter ion with an organic anion.

In forming an image, an ink ribbon may be brought into contact with the above-described photographic printing paper of the present invention, and a thermal stimulus may be applied to the ink ribbon selectively according to an image signal. FIG. 2 shows an example of such an image forming method. That is, an ink layer 13 containing a cationic dye, a film substrate 14 and a heat resistant slipping layer 15 are sequentially laminated on a photographic printing paper 10 of the present invention comprising a white support 11 and a dye receiving layer 12 laminated thereon. The ink layer 13 of the formed ink ribbon 20 is replaced with the dye receiving layer 1 of the printing paper 10.
It is pressed against 2, and a thermal stimulus is given by a heating means, for example, the thermal head 16. As a result, the cationic dye contained in the ink layer 13 is rapidly transferred and transferred to the dye receiving layer 12 of the photographic printing paper 10 to form a dye image.

The means for applying a thermal stimulus to the ink ribbon is not limited to the thermal head, but various heating means proposed so far in the thermal transfer system can be used.

[0043]

The clay organic composite used in the dye receiving layer of the photographic paper of the present invention is a 2: 1 type silicate mineral, and the two silica tetrahedral layers are magnesium octahedral layers or aluminum octahedral layers. It has a structure in which several to several tens of silicate layers having a sandwich type three-layer structure with layers sandwiched therebetween are laminated. Interlayer water and interlayer ions (usually, alkali metal ions that are exchangeable ions) are held between the layers. This state is shown in FIG. That is, the swellable layered silicate 1 holds exchangeable ions 2 between layers. The interlayer distance at this time is d1.

When the swellable layered silicate 1 is swollen with water and an organic cation, for example, a quaternary ammonium ion 3 having a hydrophobic chain is added, ion exchange as shown in FIG. The quaternary ammonium ion 3 is incorporated between the layers instead of the sex ion 2 to form the clay organic composite 4. Thus, the clay-organic composite 4 having the quaternary ammonium ion 3 having a hydrophobic chain held between the layers
Will swell when mixed and dispersed in a non-aqueous polymer binder, and has an affinity for the polymer binder.

Further, the interlayer distance d of the clay organic composite 4
2 is the interlayer distance d1 of the swelling layered silicate before the quaternary ammonium ion 3 is incorporated between the layers (Fig. 1).
It becomes larger than (a)), and the clay-organic composite has ion exchange ability with the cationic dye.

In the present invention, the swellable layered silicate to which the ion exchange ability has been imparted in this way is further subjected to an acid treatment. Alternatively, as the swellable layered silicate, one that has been subjected to an acid treatment before being imparted with an ion exchange ability is used. By this acid treatment, the liquid property of the dispersion liquid in which the swellable layered silicate is dispersed in water is changed from basic to weakly basic to acidic, whereby impurities between layers of the swellable layered silicate are removed. As a result, the ion exchange capacity is further improved, and the force for incorporating the cationic dye between the layers is increased. Therefore, by using such a clay organic composite 4 in the dye receiving layer of the printing paper, it is possible to increase the density of the image formed on the printing paper and further improve the fixing property of the image.

The clay-organic composite 4 is mixed and dispersed in a non-aqueous polymer binder to form a dye receiving layer of photographic paper, and an ink ribbon containing a cationic dye, preferably a hydrophobic cationic dye is used for the dye receiving layer. When heat-sensitive transfer recording is performed, the cationic dye contained in the ink layer of the ink ribbon is rapidly transferred to the dye receiving layer of the printing paper and transferred. The transferred cationic dye is compatible with the non-aqueous dye receiving layer and at the same time also enters the layer of the swollen clay organic composite 4. Then, as shown in FIG. 1 (c), ion exchange occurs between the quaternary ammonium ion 3 and the cationic dye 5 between the layers of the clay organic composite 4, and the cationic dye 5 is transferred between the layers of the clay organic composite 4. It is captured. And
Cationic dye 5 incorporated between layers of clay-organic composite 4
Forms an ionic bond with the clay-organic composite to form a dye image firmly fixed on the dye receiving layer.

When a polymer binder having a refractive index similar to that of the clay organic composite 4 is used as the polymer binder constituting the dye receiving layer, the color saturation of the dye image formed on the dye receiving layer is increased. Is possible.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Synthesis Example [Preparation of Synthetic Smectite] 4 liters of water was placed in a 10 liter beaker to dissolve 860 g of No. 3 water glass, and 162 g of 95% sulfuric acid was added all at once with stirring to obtain a silicate solution. . Next, 560 g of magnesium chloride was dissolved in 1 liter of water, and this was added to the silicate solution to prepare a homogeneous mixed solution.

This homogeneous mixed solution was added dropwise to 3.6 liters of 2N-sodium hydroxide solution over 5 minutes while stirring. The reaction precipitate obtained was immediately filtered and washed with a cross flow type filtration system manufactured by NGK Insulators, Ltd., and then 200 ml of water and 1 part of lithium hydroxide.
A solution of 4.5 g was added to make a slurry.

The slurry was transferred to an autoclave and 2
Hydrothermal reaction was performed at 6 Kg / cm ² and 225 ° C. for 3 hours.
After cooling, the reaction product was taken out, dried at 80 ° C., and pulverized to obtain a synthetic smectite of the following formula (2).

[0053]

_{Embedded image} Na _0.5 Mg _2.9 Li _0.4 Si ₄ O ₁₀ (OH) ₂ (2) The cation exchange capacity of this synthetic smectite was 101 meq / 100 g.

Example 1 [Preparation of Clay Organic Complex] Using the synthetic smectite prepared in the Synthesis Example, a clay organic complex A was prepared as follows.

First, 20 g of synthetic smectite was dispersed in 1 liter of water and swollen to obtain a suspension. To this suspension, 120 ml of 0.5N sulfuric acid was added and stirred, 50 ml of ethanol was further added, and while stirring, 2
13.2 g of tetra-n-decyl ammonium bromide dissolved in 00 ml of ethanol was added, and the mixture was reacted at 30 ° C. for 24 hours while stirring. The product was subjected to solid-liquid separation, washed with ethanol to remove by-product salts, and then dried to obtain a clay organic complex A.

[Preparation of printing paper] The following components of the dye-receiving layer-forming coating material were mixed using a sand mill to prepare a dye-receiving layer-forming coating material.

(Dye Receptive Layer-Forming Coating Composition) Clay Organic Complex A 4 parts by weight Vinyl chloride-vinyl acetate copolymer 4 parts by weight (Denka vinyl # 1000 GK, manufactured by Denki Kagaku Kogyo Co., Ltd.) Solvent (toluene / MEK = 1/1) 92 parts by weight

On the other hand, synthetic paper (Yupo FPG-
150, manufactured by Oji Yuka Synthetic Paper Co., Ltd. was prepared, and the above-mentioned coating for forming the receiving layer was dried to a dry thickness of 4 using a wire bar.
μm was applied and dried to prepare photographic paper.

Example 2 [Preparation of Clay Organic Complex] Using the synthetic smectite prepared in the Synthesis Example, a clay organic complex B was prepared as follows.

First, 20 g of synthetic smectite was dispersed in 1 liter of water and swollen to obtain a suspension. Add an equal volume of ethanol to this suspension and stir 2 more times.
13.2 g of tetra-n-decyl ammonium bromide dissolved in 00 ml of ethanol was added, and the mixture was reacted at 30 ° C. for 24 hours while stirring. The product is subjected to solid-liquid separation, washed with ethanol to remove by-product salts, and then 0.25
Disperse in 400 ml of N-sulfuric acid, then separate solids,
It was dried to obtain a clay organic composite B.

[Preparation of Printing Paper] A printing paper was prepared in the same manner as in Example 1 except that the clay organic composite B was used in place of the clay organic composite A.

Example 3 A clay organic composite was prepared in the same manner as in Example 2 except that 13.2 g of tetra-n-decyl ammonium bromide was replaced with 15.4 g of tetra-n-dodecyl ammonium bromide in preparing the clay organic composite. The body C was prepared, and the clay organic composite C was used to prepare photographic paper.

Comparative Example 1 A clay organic composite was prepared in the same manner as in Example 1 except that the synthetic smectite prepared in the synthesis example was not subjected to acid treatment with sulfuric acid to prepare a photographic paper.

Evaluation A thermal transfer printer (UP-300) was prepared by using an ink ribbon for the printing papers produced in Examples 1 to 3 and Comparative Example 1.
0, manufactured by Sony Corporation) was used to print a solid image.

In this case, as the ink ribbon, an ink layer containing a hydrophobic cationic dye was prepared and used as follows. That is, an ink layer coating liquid having the following composition was prepared.

[Composition of ink layer coating liquid] (parts by weight) Hydrophobic cation dye (C.I.Basic Blue75 lauryl sulfate) 1 Butyral resin (6000-CS, manufactured by Electrochemical Co., Ltd.) 1 Toluene 12 MEK 12

A PET film having a thickness of 6 μm was prepared as a base film, and the above-mentioned ink layer coating liquid was applied thereon to a dry thickness of about 1 μm, and dried to obtain an ink ribbon.

As a result of printing, the images formed on the printing papers of Examples 1 to 3 were excellent in gloss and had an ideal hue of cyan. On the other hand, the image formed on the photographic printing paper of Comparative Example 1 lacked gloss and exhibited a reddish blue color, which was unsuitable for practical use.

Further, the formed image was subjected to a laminator heat treatment. This laminator heat treatment is performed using a commercially available film laminator (MS Pouch H-140, Meiko Shokai Co., Ltd.).
(Manufactured by Mfg. Co., Ltd.) was used for thermocompression bonding with a 125 μm-thick PET film superposed on the printed matter, and after returning to room temperature, the PET film was peeled off.

Next, in order to examine the fixability of these images, before and after the laminator heat treatment,
(I) Ethanol immersion test and (ii) Toluene immersion test were conducted as follows. The results are shown in Tables 1 and 2.

(I) Ethanol immersion test The image-formed photographic paper was immersed in ethanol at a temperature of 25 ° C. for 30 days.
After dipping for a second, the dye fixing rate in this case was determined by the following formula from the measurement of the optical density before and after the dipping.

Dye fixing ratio (%) = (Optical density (OD) after immersion / Optical density (OD) before immersion) × 100

(Ii) Toluene Immersion Test The image-formed photographic printing paper was immersed in toluene at a temperature of 25 ° C. for 30 seconds, and the dye fixing ratio in this case was determined in the same manner as above from the measurement of the optical density before and after the immersion.

[0074]

[Table 1] Image fixing property before laminator heat treatment Immersion in ethanol Immersion in toluene Fixing rate (%) Image density before immersion Fixing rate (%) Image density before immersion Example 1 74.3 1.67 98.1 1.62 Implementation Example 2 74.1 1.70 94.9 1.75 Example 3 79.9 1.49 100 1.43 Comparative Example 1 71.3 1.50 90.9 1.54

[0075]

[Table 2] Image fixability after heat treatment of laminator Ethanol Immersion Toluene Immersion Fixing rate (%) Image density before immersion Immobilization rate (%) Image density before immersion Example 1 99.4 1.65 95.7 1.63 Implementation Example 2 96.8 1.57 95.7 1.63 Example 3 97.9 1.46 100 1.48 Comparative Example 1 87.4 1.43 89.0 1.46 From the results shown in Tables 1 and 2, it can be seen that the photographic printing papers of Examples have extremely high dye fixing ratio.

[0076]

According to the present invention, it is possible to greatly improve the fixability of the image formed on the photographic printing paper. It is also possible to increase the saturation of the image formed on the printing paper.

[Brief description of the drawings]

FIG. 1 is an explanatory view of the action of a dye receiving layer of the present invention.

FIG. 2 is an explanatory diagram of an image forming method using a thermal transfer method.

[Explanation of symbols]

 1 Swellable Layered Silicate 2 Interlayer Exchangeable Ion 3 Quaternary Ammonium Ion 4 Clay Organic Complex 5 Cationic Dye

Front page continued (72) Inventor Yoshio Fujiwara, 6-735 Kitashinagawa, Shinagawa-ku, Tokyo, Sony Corporation (72) Inventor Toshikazu Fujisaki, 23, Ichibancho, Chiyoda-ku, Tokyo 3 Corp Corp. (72) Inventor Takahiro Sekimoto, 23, Ichibancho, Chiyoda-ku, Tokyo, 3 Corp Corp. (72) Inventor, Kazuo Ito, 23, Ichibancho, Chiyoda-ku, Tokyo, Corp., Chemical Corp.

Claims (9)

[Claims] 1. A photographic paper comprising a support and a dye-receiving layer formed thereon, wherein the dye-receiving layer has the following (I) or (II) (I) swellable layered silicate interlayer ions. Clay organic complex ion-exchanged with a cationic dye for ion-exchangeable ions, then acid-treated clay swellable layered silicate (II) is acid-treated, and then the interlayer ion of the acid-treated swellable layered silicate is cation A photographic printing paper characterized by containing a dye-exchangeable ion-exchangeable clay organic complex and a polymer binder. 2. The photographic paper according to claim 1, wherein the swellable layered silicic acid is a synthetic smectite. 3. A synthetic smectite, wherein a homogeneous mixture of silicic acid and magnesium salt is reacted with an alkaline solution to synthesize a silicon-magnesium complex, and a by-produced electrolyte is removed to obtain the obtained silicon-magnesium complex. Lithium ions, or sodium ions and / or fluorine ions together with lithium ions are added to the above, hydrothermally reacted at 100 to 350 ° C., and then dried to obtain the following formula (1): embedded image X _{0.1 to 1.0} Mg _{2.4~2.9 Li 0.1~0.6 Si 3.5~4.5 O 9.5~10.5 (} OH and / or _F) 1.5~2.5 (1) (wherein, X is an interlayer ion, represents a Li-ion and / or Na ions 3.) The photographic paper according to claim 2, which is a synthetic smectite. 4. The photographic printing paper according to claim 1, wherein the ion that is ion-exchangeable with the cationic dye, which is replacing the interlayer ion of the clay organic composite, is an organic cation. 5. The printing paper according to claim 4, wherein the organic cation is a quaternary ammonium ion or a phosphonium ion. 6. The quaternary ammonium ion has 4 carbon atoms.
The photographic paper according to claim 5, which is a quaternary ammonium ion having the above alkyl group. 7. The quaternary ammonium ion is tetra-
The photographic paper according to claim 6, which is an n-decyl ammonium ion or a tetra-n-dodecyl ammonium ion. 8. An ink ribbon containing a cationic dye is brought into contact with the photographic printing paper according to claim 1, and the cationic dye is transferred from the ink ribbon to the photographic paper by thermal stimulation to be fixed. And an image forming method. 9. The image forming method according to claim 8, wherein the cationic dye is a hydrophobic cationic dye in which a hydrophilic counter ion of the cationic dye is replaced with an organic anion.