JPS594694B2 - Colored image forming method and photosensitive colored image forming material used therein - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the recording of optical images, particularly to a material that forms a colored visible image by simple processing after exposure to actinic rays, and an image forming method using the material.

Conventionally, there has been known a photosensitive coloring material which can be developed by heating and contains a paraphenylenediamine developer and a phenolic coupler or an active methylene coupler as coloring components.

(See US Pat. No. 3,531,286″0) In this case, a small amount of silver halide is used to provide photosensitivity, and
The oxidation of phenylenediamine is carried out by an organic silver salt such as silver behenate. Although this technique is recognized as an effort to significantly simplify the color development method, it has the disadvantage that only a cloudy dye image can be obtained because dye and silver are generated simultaneously in this case.Also, Sprague et al. R.H.
Spraguetal) focused on the fact that titanium oxide can be color sensitized, and announced a method of developing with a p-phenylenediamine type developer and a solution containing a coupler to form a dye image together with a silver image.

(1969 SPSE Annual Meeting Preprint P219) In this case as well, since silver is generated, only a cloudy image is given. It is an object of the present invention to produce substantially no silver image and a dye image without forming a dye image.
The object of the present invention is to provide a new method for forming pigments that selectively produces pigments.

By reducing the amount of photosensitive silver salt and using a small amount of silver salt, the final formation of silver can be substantially avoided. However, if you do this, almost no pigment will be produced, so it will be fragrant. 0 Not. The present inventors have discovered that dye formation can occur efficiently by bringing a small amount of photosensitive silver salt into contact with a catalyst carrier, and have accomplished the present invention. That is, the present invention provides the following features: 1. On a support, (a) a catalyst carrier, (b) a photosensitive silver salt in contact with component (a), and (c) reacting with the oxidized component (d). After image exposure, a photosensitive colored image-forming material in which a coupler that forms a dye and (d) a color developing agent are provided in one layer or two or more layers is exposed in the coexistence of a base generator that can liberate a base by heating. Colored image forming method characterized by heat treatment; 2. On the support, (a) a catalyst carrier, (b) a photosensitive silver salt in contact with component (a), (c) a coupler that reacts with the oxidized component (d) to form a dye, (d ) color developing agent, (
e) A photosensitive colored image forming material in which a base generator is provided in one layer or divided into two or more layers; 3. On the support, (a) a catalyst carrier, (b) a photosensitive silver salt in contact with component (a), (c)
a coupler that reacts with the oxidized component (d) to form a dye, (d) a color developing agent, (e) a base generator, and
(f) A photosensitive colored image forming material in which a moisture supplying agent is provided in one layer or in two or more layers.

As the catalyst carrier for component (a) used in the present invention, a colorless or light-colored solid substance can be used.

Supports commonly used in the field of catalysts can be used. Those with strong adsorption properties and strong photo-oxidation properties are preferred. Specifically, the following compounds can be used. Alumina, silica-alumina, molybdenum trioxide,
titanium dioxide, tungsten trioxide, antimony oxide,
Germanium oxide, cerium oxide, sodium oxide, bismuth oxide, vanadium trioxide, vanadium pentoxide, selenium dioxide, tellurium dioxide, SlO2/Al2O3, Zn
O-Cr2O3, Al2O3B2O3, B2O3・Ti
O2, ThO2・MgO, Cr2O3-Al2O3, C
r2O3-ZnO. cuOseO2, CUO-ZnO.
Al2O3-K2O, Fe2O3-ZnO, SiO2・
MgO. MOO3-Al2O3, MOO3-Bl2O3
-P2O5-SiO2, MOO3-WO3, MOO2-
SiO2, NiOAl2O3, NiS-SlO2-Al
2O3, SiO2zrO2, ThO2・ZnO, ThO
2- Oxides such as Al2O3, sulfides such as zinc sulfide, selenium sulfide, etc., hydroxides such as zinc hydroxide, aluminum hydroxide, cadmium hydroxide, lead hydroxide, etc., barium sulfate, calcium carbonate. , zinc stearate, calcium stearate, calcium silicate, sodium aluminate, calcium tungstate, barium molybdate, calcium phosphate, barium phosphate, activated clay, etc.

On the other hand, as the photosensitive silver salt of component (b) used in the present invention, phenyl silver. 2:1 complex of silver nitrate (2C6H5A
g-AgNO3), phenylethynyl silver, triethylphosphine complex (C6H5CCAg-P(C2H5)3)
, 1,5,9-cyclododecanetriene. Silver nitrate 1:
Organic silver compounds such as 2 complexes, silver salts of organic acids such as silver acetate, silver propionate, silver oxalate, silver pelargonate, silver salicylate, silver lactate, etc., silver perchlorate, silver chromate, tungsten Silver salts of inorganic acids such as acid silver, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloroiodobromide, etc., etc. be.

Among these photosensitive silver salts, silver halide gives particularly preferable results in terms of photosensitivity and stability.

The photosensitive silver salt of component (b) needs to be in contact with the catalyst carrier of Seishu a), but no special measures are required for this purpose. For example, titanium dioxide as component (a) and component (b).
When silver halide is used as a silver halide, silver ions are allowed to act on titanium halide to partially convert it into silver halide.
Next, it can be carried out by a method in which only titanium halide is replaced with titanium oxide, or by a method in which component (a) and component (b) are mixed in advance and then mixed with other components.

The coupler of component (c) used in the present invention, and the coupler of component (
The color developing agent d) can be any of those used in the formation of color images using silver halide color photosensitive materials. For example, C. E. K. "Photograph Process" by Mies, 3rd edition, Chapter 17; P. W.
Vitam et al., Journal of Photographic Science, Vol. 6, p. 157 (1958); Kimura and Yoshida, “Journal of the Society of Organic Synthetic Chemistry, Vol. 23, p. 989 (1958);
1965); J. S. It is described in "History of Color Photography" by Breedmatsu, published by The Focal Press (1968), etc. Useful examples of color developing agents include the following compounds. D-14-amino-N-N-diethylaniline D-24-amino-N-N-diethyl-3-
Methylaniline D-34-amino-N-N-diethyl-
3(β-hydroxyethyl)aniline D-44-amino-N-N-bis(β-hydroxyethyl)-3-methylaniline D-54-amino-N-ethyl-3-methylN-(β-methylsulfone amidoethyl)aniline D-64-amino-N-ethyl-N-(β-hydroxyethyl)aniline D-7 N-(4-aminophenyl)
Piperidine D-84-amino-N-N-diethyl-2-
Methylaniline D-94-amino-N-N-diethyl-
3-Methoxyaniline These may be used in free form or in the form of salts such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, benzenesulfonate, and naphthalene disulfonate. Good too.

Further, as couplers that can be used in the present invention, in silver halide color photographic materials, both those that are contained in the photographic material (so-called diffusion-resistant couplers) and those that are added to the developer can be used. Diffusion resistant couplers are preferred.

Useful examples of couplers include the following compounds: C-1N-(p-toluenesulfonyl)-N(benzoylacetyl)-p-phenylenediamine C-2N-(p-stearoylaminobenzoylacetyl)aniline-3,5-dicarboxylic acid C-3N-(3,5 -di-t-amylphenoxyacetyl)-N'-(benzoylacetyl)-m-phenylenediamine C-4N-(3,5-di-Sec-amylphenoxyacetyl)-ma-(benzoylacetyl) )-m-phenylenediamine C-51-phenyl-3-[4'-nitrobenzamide]-5-pyrazolone C-61-(2',4'-dimethyl-5'-chlorophenyl)-3-(m- palmitylphenoxy-α-bunaryl amino)-5-pyrazolone C-7 1-phenyl-3-[m-(p-Tertamylphenoxy)benzamide]5-pyrazolone C-81-phenyl-3-[m-(p -Secamylphenoxy)benzamide]5-pyrazolone C-91-[p-(3,5-dimethylphenoxy)phenyl]-3-(4'-Tert-amyl-3-methylbenzamide-5-pyrazolone C-101 -[p-(3,5-dimethylphenoxy)phenyl]-3-(4'-Sec-amyl-3-methylbenzamide)-5 pyrazolone C-111-[p-(3,5-dimethyl J Gnoxy)phenyl]-3-(4'-amyl3'-methylbenzamide)-5-pyrazolone C-122,6-dibromo-1,5-naphthalenediol C-13N~butyl-1-hydroxy-2-naphthamide C-14N-lauryl-1-hydroxy-2-naphthamide C-15N-octadecyl-1-hydroxy-2-
Naphthamide C-16N-[{1'-(N-methyl-N
-octadecyl)amino-5'-sulfo}phenyl]-
1-Hydroxy-2-naphthamide C-17N-(1-hydroxynaphthol)(0-acetylamino)phenylethylamine C-18N-[γ-(2,4-di-Tert-amylphenoxy)propyl]-2-naphthamide C-19N-[γ-(2,4-di-Sec-amylphenoxy)propyl]-2-naphthamide The above four components are preferably dispersed in a binder and provided on a support to form the coloring agent of the present invention. An imaging material is obtained.

Binders include hydrophobic polymers such as polystyrene, polymethyl methacrylate, polyvinyl butyral, polyvinylidene chloride, polyvinyl acetate, and polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, gelatin, hydroxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl methacrylate, and acrylic acid. Hydrophilic polymers such as copolymers of , casein, starch, and gum arabic can be used.

As the support, paper, plastic film, metal plate, etc. can be used.

Specific examples include photographic baryta paper, synthetic paper, polyester film, cellulose acetate film, and aluminum plate. Alternatively, a composite film may be used. The ratio of each component constituting the colored image forming material of the present invention is 1 to 10 parts by weight of the photosensitive silver salt to 1 part by weight of the catalyst carrier.
3 parts by weight, preferably 0.1 to 0.01 parts by weight,
The color developing agent is 10 to 10-2 parts by weight, preferably 1 to 10-2 parts by weight.
0.2 parts by weight, and the coupler of component (c) is 102~
10@-1 parts by weight, preferably in the range from 2 to 0.2 parts by weight.

In addition, the binder is added in an amount of 10 to 1 part by weight per 1 part by weight of the catalyst carrier.
It is used in an amount of 0-2 parts by weight, preferably in a range of 4 to -2 parts by weight.
In the present invention, Seishu a), (b) and Seishu c),
(d); Components (a), (b), (c) and Seishu d), or components (a), (b), component (c) and Seishu d) each as separate layers on a support. It can also be provided in

The colored image forming material of the present invention can contain various compounds in addition to these basic compositions.

Examples include stabilizers for color developing agents (eg, hydroxylamine sulfate, dihydroxyacetone, etc.), color sensitizers (sensitizing dyes, etc.), and chemical sensitizers. The thickness of the photosensitive layer after drying is suitably in the range of 3 to 30 microns. The colored image forming material of the present invention may be provided with a protective layer on the photosensitive layer in order to protect the photosensitive layer.

As the protective layer, a polymer layer having a thickness of 1 to 20 microns is suitable.

Suitable polymers include, for example, polyvinyl chloride, polyvinyl acetate, copolymers of vinyl chloride and vinyl acetate,
Polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, xylene resin, benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinylidene chloride, chlorinated polypropylene, polyvinyl pyrrolidone, polycarbonate, cellulose propionate, Examples include polyvinyl formal, cellulose acetate phthalate, and cellulose acetate propionate.

Next, the image forming method of the present invention will be explained.

The light-sensitive material is thermally developed in the presence of a base generator capable of liberating a base by heating. Heat development becomes possible by the coexistence of a base generator. That is, upon heating by suitable means, a dye image is produced in the previously exposed areas. The heating temperature is in the range of 70°C to 250°C, especially 80°C.
A range of 15°C to 15°C is preferred. As the base generator, compounds known in the field of diazo copying can be used. For example, adducts of organic amines and halogen-substituted bisphenols (Japanese Patent Publication No. 39-10200), fusible bases (Japanese Patent Publication No. 39-18704), urea (Japanese Patent Publication No. 18704-1970),
-12826), ammonium salts of urea and weak acids (Special Publication No. 1699/1973), fatty acid amides and fatty acid metal salts (
(Japanese Patent Publication No. 4415747), adducts of organic amines and substituted coumaron (Japanese Patent Publication No. 19235-1977), adducts of germanium halides and organic amines (Japanese Patent Publication No. 471496)
0), hexamethylenetetramine, semicarbazide (
U.S. Pat. No. 3,157,503), etc.

The base generator may be supplied from the outside or may be incorporated into the sensitive material in advance.

When supplying from outside, it is preferable to use a solution of a base generator dissolved in an appropriate solvent such as an aqueous solution. Furthermore, when adding the base generator to the photosensitive layer in advance, care must be taken in how the base generator is added. This is because fog is likely to occur. In a preferred embodiment, a base generator layer is provided as a layer separate from the photosensitive layer. When the base generator is contained in the photosensitive layer, the amount used is suitably 10-1 to 100 parts by weight, preferably 0.05 to 10 parts by weight, per 1 part by weight of the catalyst carrier. In addition, when introducing from the outside, for example, the solution (especially aqueous solution) is 0.1 to 70% by weight, preferably 3 to 2% by weight.
A 0% by weight solution is used. The colored image forming material of the present invention preferably contains a moisture supplying agent. The moisture supply agent refers to a compound that can release moisture upon heating.

For example, sodium acetate trihydrate, lead acetate trihydrate, zinc acetate dihydrate, magnesium acetate tetrahydrate, sodium phosphate 1
These include compounds containing water of crystallization such as dihydrate and sodium sulfate decahydrate, clay/bentonite, and polyethylene glycol. When a compound containing water of crystallization is dispersed in an aqueous binder solution such as an aqueous gelatin solution, even if it is added in a form containing water of crystallization or in an anhydrous form, the water of crystallization will eventually be contained in the sensitive material. Therefore, it is possible to obtain equivalent results even when actually compared. The moisture supply agent is
10-1 to 20 per part by weight of the catalyst carrier of component (a)
0 parts by weight is suitable, and 0.5 to 30 parts by weight is more preferable. By adding a base generator and a moisture supply agent,
Development is possible simply by heating.

By using the colored imaging materials of this invention any desired color image can be achieved by selecting a color forming coupler. Furthermore, a black image can also be obtained by using a suitable combination of couplers that give a yellow image, couplers that give a magenta image, and couplers that give a cyan image. Multicolor images may also be provided using the principles of the present invention. That is, a first layer on the support contains a coupler and a color developing agent suitable for producing a cyan dye, which is sensitive to red light, and a second layer is sensitive to green light, producing a magenta dye. The third layer is a yellow filter layer that prevents the passage of ultraviolet and blue light, and the top layer is a coupler and color developing agent that is sensitive to blue light and produces a yellow dye. A photosensitive material consisting of a layer containing a developing agent. In addition, the layer that is sensitive to the three colors of blue light, green light, and red light and forms a color image can be provided as microscopic spots arranged separately, and a structure may be used in which appropriate filters are installed where necessary. good. Multicolors can be easily reproduced by contact printing onto such color-forming photosensitive materials, or by exposing a multicolor transparent original to light using an appropriate projection device and then performing alkali treatment. can.

Effects and advantages obtained by the present invention will be listed below.

(1) High sensitivity is possible because silver salt is used as a photocatalyst. (2) Since only a catalytic amount of silver salt is used, only the dye is selectively produced, so there is no need for a desilvering step, and sharp images can be obtained.

(3) Can be developed with simple processing.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is of course not limited to these.

Note that % indicates weight % unless otherwise specified. Example 1 50ml of 6% gelatin, 1TfL1 of 1% sodium dodecylsulfonate aqueous solution, and Toray Silicone SH55O3
(manufactured by Toray Silicone Co., Ltd.), and further added zinc oxide 17 and 0.4% potassium bromide aqueous solution 8me.
Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 50
Stirred at ~60°C for 1 minute at approximately 3000 rpm.

Further, 8 ml of 0.5% silver nitrate aqueous solution was added to this mixture while stirring was continued, and after stirring for 1 minute, 0.5y of the compound C-16 coupler was added and stirred for 1 minute. Finally, 0.3y of the sulfate of compound D2 was added and stirred. The resulting emulsion was applied to baryta paper and dried. Film thickness when dry is approximately 20
．． It was a. This photosensitive material was mixed with the following base generator solution.
After 0 seconds of treatment, 35 CTI from a 250 watt ultra-high pressure mercury lamp.
Exposure for 0.2 seconds through a photographic negative at a distance of L, 140
It was heated at .degree. C. for 30 seconds to obtain a blue-green image in the exposed area.

In order to clarify the effects of the base generator solution catalyst carrier, etc., the following experiment was conducted and compared with Example 1.

A photosensitive material was prepared and processed in exactly the same manner as in Example 1, except that zinc oxide was omitted, but only a low-density gray image was obtained.

It was found that the presence of zinc oxide allows the pigment-forming reaction to occur uniformly. On the other hand, a photosensitive material was prepared and processed in the same manner as in Example 1 except that silver bromide, which is thought to be a photosensitive component, was removed, but in this case no photoresponse was observed. I couldn't help it.

Zinc oxide is well-known as a photocatalyst, but in this case it can be seen that silver bromide acts as a photocatalyst and zinc oxide does not act as a photocatalyst. Alternatively, an image can be obtained by making a photosensitive material without the coupler and processing it in the same way. In this case, it is thought that the oxidized product of the reducing agent compound contributes to color development. This simply shows that it is possible to obtain records without a coupler.
A colored image as shown below was obtained by using the same amount of the following compound in place of the coupler of Compound C-16.

Example 1 ml of 1% sodium dodecyl sulfonate aqueous solution and 310 drops of Toray Silicone SH55O were added to 50 ml of 77% gelatin aqueous solution, and 1.5 y of titanium oxide was added.
and 0.05y of lead monoxide, and 1% sodium bromide aqueous solution
0ml was added and emulsified and dispersed in the same manner as in Example 1.

While stirring, add 10 ml of 1.2% silver nitrate aqueous solution,
After stirring for 90 seconds, 0.7 y of the coupler of Compound C-6 and 0.3 V of the hydrochloride of Compound D-1 were added, and after emulsifying and dispersing, 5 ml of dibutyl phthalate was added and emulsifying and dispersing in the same manner. This emulsion was coated on a polyester film to a dry coating thickness of approximately 1.
It was applied to a thickness of 5 microns and dried. This light-sensitive material was exposed for 10 seconds through a photographic negative at a distance of 35 (7 IL) from a 250 W ultra-high pressure mercury lamp.
A magenta image was obtained by treating with a 0% aqueous solution and heating at 135° C. for 60 seconds.

Example 8 An emulsion was prepared, coated on baryta paper, and dried.

The thickness of the photosensitive layer after drying was 20μ. This photosensitive material was treated with the base generator of Example 1, exposed for 1 second through a photographic negative at a distance of 40 degrees from a 300 Watt photographic flat wrap, and then heated at 110°C for 90 seconds to produce a blue-green color. Obtained a statue of. Example 9 To 50 ml of 6% gelatin, add 1 ml of 1% sodium dodecyl sulfonate aqueous solution and Toray Silicone SH55O310 drops, and further add 17 zinc oxide, 0.37 bismuth oxide, 0
．． 8 ml of a 4% potassium bromide aqueous solution was added, and the mixture was stirred for 1 minute at about 3000 rpm at a temperature of 55°C to 60°C using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).

Further, 8Tn1 of a 0.5% silver nitrate aqueous solution was added to this mixture while stirring, and after stirring for 1 minute, compound C-15 was added.
of coupler 0.57 and polyethylene glycol (molecular weight 4000) 1.47 and at about 4000 rpm.
Stir for a minute. Next, 0.37 ml of sulfate of Compound D-2 was added and stirred. Finally, sodium acetate. Sanhydrate salt 57
An aqueous solution 4Tn1 containing morpholine oxalate 17 was added and stirred. The resulting emulsion is applied to baryta paper. Dry.
The thickness of the photosensitive layer after drying was about 20 microns. This photosensitive material was exposed for 0.2 seconds through a photographic negative from a 250 watt ultra-high pressure mercury lamp at a distance of 35 cfn, and then
Heating was performed for 0 seconds, and a blue-green image was obtained in the exposed area.

A colored image as shown below was obtained by using the following compound in place of the coupler of compound C-15.

An emulsion was prepared and dried on a polyester base to a dry coating thickness of about 15 chrome.

Flat run for photography with this photosensitive material at 300 watts: to 40 watts
(Exposure for 3 seconds through a photographic negative at a distance of 1-J mo V1,
Next, it was heated at 120° C. for 1 minute to obtain a bluish-green color A.

Claims (1)

[Scope of Claims] 1. On a support, (a) a catalyst carrier, (b) a photosensitive silver salt in contact with component (a), (c) an oxidized component (d)
Coexistence of a base generator capable of liberating a base by heating after image exposure of a photosensitive colored image-forming material in which a coupler that reacts with a dye to form a dye and (d) a color developing agent are provided in one layer or two or more layers. A colored image forming method characterized by subjecting the bottom to a heat treatment. 2 On the support, (a) catalyst carrier, (b) photosensitive silver salt in contact with component (a), (c) oxidized component (d)
A photosensitive colored image-forming material comprising a coupler that reacts with a dye to form a dye, (d) a color developing agent, and (e) a base generator, which are divided into one layer or two or more layers. 3 On a support, (a) a catalyst carrier, (b) a photosensitive silver salt in contact with component (a), (c) an oxidized component (d)
A photosensitive colored image-forming material comprising a coupler that reacts with a dye to form a dye, (d) a color developing agent, (e) a base generator, and (f) a water supply agent, which are divided into one layer or two or more layers.