JPH0326376B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming method, and more particularly to a method for obtaining a non-silver salt photographic image from a photosensitive material containing a photosensitive cuprous halide salt or a photosensitive copper oxide. Silver halide photography is the most well-known metal salt photography method. This silver halide photography method is explained in detail, for example, in ``The Theory of Photographic Processes'' (Macmillan NY 1966) by C. E., K., Mies, T., Etsch, and James. The above silver halide photography method has high sensitivity, high quality,
In addition to advantages such as the ability to freely adjust intermediate tones, it also has features such as rapid processing or dry processing. In the case of silver salt color photography, since metallic silver is also used as an intermediate medium for dye image formation, it is generally necessary to use a large amount of silver. On the other hand, only a portion of used silver (silver used in image formation, silver eluted into processing solutions) can be recovered and reused.
This makes silver halide photography generally expensive. In addition, the current situation in which there is concern about the depletion of silver resources and significant fluctuations in the price of silver are also disadvantages of silver halide photography. Therefore, there is a need to develop a photographic method that uses less silver or no silver salt at all. From this point of view, many non-silver salt photography methods have been reported, but they generally have lower sensitivity than those using silver, and many non-silver salt photographic materials do not produce images with continuous gradations. I can't get it. Among non-silver salt photosensitive materials, the photographic method using cuprous halide fine grain crystals is the No. 1 research disclosing material that has relatively high sensitivity and can produce images with continuous gradation. It is described in .15166 and No.15252 etc. According to these documents, cuprous halide crystals are sensitive to ultraviolet light, and a photosensitive material obtained by coating a dispersion of the crystals in a binder solution on a support is sensitive to ultraviolet light. After irradiation, a colored image with continuous gradations is obtained by developing with a physical developer or a chemical developer. The development method for the light-sensitive material was studied by Harry T. Spencer, Y. Hill et al., and the details are described in Research Disclosure No. 15166 (1976). That is, cuprous halide crystals are dispersed in a binder solution soluble in an organic solvent (acetone, etc.) such as cellulose acetate butyrate, coated on a support, and dried to produce a cuprous halide photosensitive material. Photosensitize the material in a wet state by immersing it in a polar solvent such as water, alcohol, or glycol, or in a developer solution in which an alkyl amine such as ethylenediamine, diethylenetriamine, or triethylenetetraamine is dissolved in the polar solvent, or in a dry state. When the cuprous halide photosensitive material that has been subjected to a treatment to impart the same properties to light is exposed in a dry state, the following disproportionation reaction occurs, producing metallic copper and Cu ²⁺ ions. 2Cu ⁺ →Cu ⁰ +Cu ²⁺ (1) When a photosensitive material that has produced metallic copper upon exposure is developed with a developer containing the above alkylamine,
A Cu ²⁺ ion complex is formed with the alkylamine, and metallic copper exhibits a catalytic effect on the disproportionation reaction, and the disproportionation reaction rapidly progresses in the area where metallic copper is present due to exposure. Then, development is performed to obtain a visible image. However, in the development process using the developer, (1) the fog density of the colored image obtained by development (the color density of the unexposed area) is high. (2) The contrast of the image obtained by the development is low. (3) There is a drawback that the Cu ²⁺ -alkylamine complex formed during development is eluted into the developer, resulting in extremely strong coloring of the developer. Therefore, images obtained by development with an alkylamine solution have a high fog density and lack contrast, and cannot be used as photographic images. The present inventors conducted extensive research to solve the various problems of developing solutions for the above-mentioned cuprous halide photosensitive materials, and were able to accomplish the present invention. A first object of the present invention is to provide an image forming method using a novel developing means for a copper salt photographic light-sensitive material, by which a photographic image with low fog, high maximum density, and high image contrast can be obtained. A second object of the present invention is to provide a developer for copper salt photographic materials, which provides photographic images with low fog, high maximum density, and high image contrast. As a result of extensive research into the above-mentioned problems, the present inventors have discovered that a layer in which photosensitive copper halide (1) or photosensitive copper oxide (1) is dispersed in a binder or a layer in which photosensitive copper oxide (1) An image forming method in which a photosensitive material having on a support a layer consisting of substantially the following is imagewise exposed and then developed, the method comprises the following general formula (),
It has been found that the above object can be achieved by an image forming method in which a copper image is formed by developing with a solution containing the compound represented by () or (). general formula

【formula】

【formula】

In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
aminoalkyl group, hydroxyaminoalkyl group having 1 to 4 carbon atoms, -(CH ₂ ) _o COOH, -(CH ₂ ) _o
CONH (where n represents an integer from 1 to 4),

【formula】

[Formula] (where m represents an integer from 1 to 3) - (CH ₂ ) _o NHCONH ₂ (where n is 1
~ represents an integer of 4),

[Formula] (where q represents an integer of 1 to 2),

[Formula] (where n is 1 to 4) (representing an integer),

[Formula] Also teeth

[Formula], R ₂ is -OM (where M represents a hydrogen atom or an alkali metal atom), -NH ₂ , or NHR ₅ (where R ₅ has 1 to 1 carbon atoms)
6 alkyl group, a hydroxyaminoalkyl group having 1 to 4 carbon atoms, or an aromatic amine), R ₃ and R ₄ may be the same or different, and each represents a hydrogen atom, a hydroxyaminoalkyl group having 1 to 6 carbon atoms, or an aromatic amine. an alkyl group,
a hydroxyalkyl group having 1 to 4 carbon atoms,

[Formula] (where l represents an integer from 0 to 4), -CO(CH ₂ ) _l CH ₃ (however, l represents an integer from 0 to 4), or -CO(CH ₂ ) _o NH ₂ (however, n is 1
represents an integer of ~4), and Y is −
CH ₂ CHR ₆ CH ₂ − (where R ₆ represents a hydrogen atom or a hydroxyl group), Z is −(CH ₂ ) _p (where p
represents an integer from 4 to 6). The present invention will be explained in more detail below. First, the layer in which photosensitive cuprous halide is dispersed in a binder used in the present invention is a layer in which photosensitive cuprous halide microcrystals are dispersed in a binder made of a polymer compound such as gelatin. This is the layer that exists. Examples of the method for forming this layer include the method described in Research Disclosure No. 15166. That is, as a method for producing cuprous halide crystals, there is a method described in R.N. Keller, H.D. Vaikov, "Inorganic Synthesis," Volume 1, Page 1 (1946). That is, in an acidic aqueous solution of cupric halides (cupric chloride, cupric bromide), the cupric halides are reduced by the following reaction using sodium sulfite, and the coarse cuprous halides are reduced. Can make crystals. 2CuX ₂ +Na ₂ SO ₃ +H ₂ O→2CuX + Na ₂ SO ₄ +
2HX When the large crystals of the cuprous halide obtained by this method are crushed in a ball mill and the fine powder of the crystals is redispersed in a solution of the binder dissolved in an organic solvent (e.g. acetone, acetonitrile, etc.), the cuprous halide group is crushed. A copper emulsion is obtained. In the second method, the cuprous halide coarse crystals prepared above are ground in a ball mill and then redispersed in an aqueous solution of a hydrophilic protective colloid to obtain a cuprous halide emulsion in the same manner as above. Furthermore, as a third method, in an acidic aqueous solution of a hydrophilic protective colloid, sulfurous acid or its alkali metal salt, nitrous acid or its alkali metal salt, ascorbic acid or its derivative (e.g. alkali metal salt), hydrazine or its Cuprous halide fine particles formed by reducing cupric ions with a reducing agent such as a derivative, cupric chloride, cupric bromide, or a solution of any composition of these cupric halides. Dispersing the crystals yields a cuprous halide emulsion. Next, as a fourth method, in an acidic aqueous solution of a hydrophilic protective colloid, sulfurous acid, nitrous acid, ascorbic acid or an alkali metal salt of the acid, hydrazine or a derivative thereof (e.g. phenyl hydrazine) is added.
In the presence of a reducing agent such as, an aqueous solution of copper nitrate or an aqueous solution containing copper nitrate and silver nitrate in any composition,
An aqueous solution of an alkali metal halide (potassium chloride, potassium bromide, potassium iodide, sodium chloride, sodium bromide, sodium iodide, etc.) of any composition is mixed by a single-jet method or a double-jet method; An emulsion consisting of a dispersion of cuprous halide fine grain crystals containing silver halide, which is sometimes formed by reducing cupric ions, is obtained. As detailed above, the cuprous halide emulsion used in the present invention is an emulsion obtained by dispersing previously prepared cuprous halogen crystals in a binder solution or a protective colloid solution in the presence of halogen ions. Any emulsion consisting of a dispersion of cuprous halide crystals obtained by reducing cupric ions may be used. The halogen composition of the emulsion is at least one selected from the group consisting of chlorine, bromine and iodine. Among these, those consisting of chlorine and iodine; iodine and bromine; chlorine, iodine and bromine; chlorine and bromine; chlorine; or bromine are preferred from the viewpoint of photosensitivity and developability. In addition, as a binder or protective colloid used in the emulsion, a hydrophobic polymer compound such as a synthetic polymer compound such as cellulose acetate butyrate or polyvinyl butyral, or a hydrophilic polymer compound such as gelatin, gelatin derivative, gum arabic, albumin, etc. Natural polymeric compounds such as , agar, etc., and synthetic polymeric compounds such as polyvinyl alcohol, polyvinylpyrrolidone, cellulose ether, and partially hydrolyzed cellulose acetate can be used as appropriate. The cuprous halide photosensitive material of the present invention can be obtained by coating or absorbing the emulsion having the above composition on a support. such as paper, suitable for absorbing the emulsion of
a porous support or a support suitable for coating the emulsion to form an emulsion layer, i.e. metal plates such as glass, aluminum, copper, zinc and tin;
Furthermore, conventionally used film supports such as cellulose acetate, cellulose nitrate, acetic acid, cellulose butyrate, polyethylene terephthalate, and polystyrene, as well as baryta paper, resin-treated paper, and the like can be used. Further, the cuprous oxide photosensitive material used in the development process of the present invention refers to one obtained by coating a cuprous oxide emulsion onto a support and drying it. The cuprous oxide emulsion refers to an emulsion obtained by dispersing cuprous oxide fine powder in a binder solution, but more specifically, it refers to an emulsion prepared by the following method. . That is, firstly, cuprous oxide powder is
"Anorganic Chemistry" Volume 31,
Adjustment by the method disclosed on page 326 (1902). That is, while stirring an aqueous solution containing potassium/sodium oxalate and sodium hydroxide, an aqueous solution containing cuprous chloride and sodium chloride is slowly added to the aqueous solution, and the obtained solid cuprous oxide is obtained. Cuprous oxide powder can be obtained by washing with water and drying. This emulsion is obtained by pulverizing the cuprous oxide powder in a ball mill and redispersing the powder in a solution in which a binder is dissolved in an organic solvent (eg, acetone, acetonitrile, etc.). Second, it is an emulsion obtained by pulverizing the cuprous oxide powder prepared by the above method in a ball mill and then redispersing it in an aqueous solution of a protective colloid. It may also be a photosensitive material prepared by a method of forming a Cu ₂ O film on a support by oxidation sputtering in an atmosphere with an Ar/O ₂ pressure ratio of 1/4 using oxygen-free copper as a target. As the support used in the photosensitive material, metal substrates such as glass, aluminum, copper, zinc and tin can be used. The photosensitive material according to the present invention produced according to the preparation method described in detail above is imagewise exposed in a dry or wet state, and developed by the development method described below. Light sources used for image exposure include visible light such as tungsten lamps, xenon lamps, mercury lamps, carbon arcs, halogen lamps, and/or
and various light sources that generate ultraviolet light are used,
Exposure may be performed by printing through the original or by reflection printing. Among the light-sensitive materials used in the present invention, in the case of a light-sensitive material made only of cuprous halide and containing no silver halide, as described in Research Disclosure No. 15166 (1976), In a dry state, the photosensitivity is extremely low and there is virtually no photosensitivity, so even if imagewise exposure and development are performed in a dry state, a colored image cannot be obtained. However, since it has photosensitivity in a wet state, an image can be obtained by imagewise exposure and development in a wet state. When the cuprous halide photographic light-sensitive material is wetted, a polar solvent such as water, an alcohol such as methanol or ethanol, or a glycol such as ethylene glycol or diethylene glycol, or a developer in which a developer is dissolved in the solvent is used. May be moistened. On the other hand, since a photosensitive material made of cuprous halide containing silver halide has photosensitivity in a dry state, it may be imagewise exposed in a dry state. The imagewise exposed photosensitive material can be developed using a developer consisting of an alkaline solution containing at least one compound selected from the group of compounds represented by the general formula (), (), or (). . Specific examples of the compounds represented by the general formula (), (), or () used as a developing agent in the developer include the following.

【table】

【table】

【table】

[Example 1]

A copper iodobromide emulsion was prepared using a solution with the following composition. (Solution 1) Pure water gelatin 1000ml 50gr (Solution 2) Pure water KBr KI L-Ascorbic acid 1575ml 85.7gr 2.2gr 79.2gr (Solution 3) Pure water Cu (NO ₃ ) ₂ 3H ₂ O 2000ml 106gr (Solution 1) While keeping the liquid temperature at 45℃ and stirring,
Addition of (solution-2) and (solution-3) is started simultaneously. (Solution-2) was added over 20 minutes, and one (Solution-3) was added over 22 minutes. The temperature during physical ripening was kept at 45°C. After all of (Solution-3) was added, physical ripening was continued for 10 minutes. Thereafter, desalination and water washing were performed by the following operations. As a precipitant, Demol, manufactured by Kao Atlas Co., Ltd.
A 5% N aqueous solution and a 30% aqueous magnesium sulfate solution were added at a ratio of 1:7 until precipitation occurred. After the precipitate has settled by standing still, the supernatant is decanted and poured with distilled water.
3000ml was added to redisperse the precipitate. A 30% aqueous magnesium sulfate solution was added again until a precipitate was formed.
After the crystal particles had settled, the supernatant was decanted, an aqueous ossein gelatin solution (containing 45 grams of gelatin) was added, and the mixture was dispersed by stirring at 40° C. for 30 minutes, and the total volume was adjusted to 1000 ml with distilled water. A hardener and a surfactant (coating aid) are added to the emulsion.
was added, coated on a polyethylene terephthalate film support, and dried at 60° C. for 30 minutes to produce a photosensitive material-A to be used in the development of the present invention. The thickness of the emulsion layer after drying was 4 μm. Furthermore, when the amount of cuprous halide contained in this photosensitive material was measured using a fluorescent X-ray method, it was found to be 32
mg/ ^100cm2 . Next, the above photosensitive material was heated at 20°C with a developer having the composition shown below and using the α-amino acid listed in the table below as a developing agent.
260~420μ in wet state after soaking for 30 seconds
A light source with ultraviolet radiation in the range of
An exposure of 10 ⁴ erg/cm ² was given. Thereafter, development was carried out at 25° C. for 3 minutes using a developer having the composition shown below, followed by fixing using a fixer having the following composition for 5 minutes or more, followed by washing with water and drying. [Developer] α-amino acid 0.13 mol Boric acid sand 2.62×10 ^-2 mol Pure water 1000 ml (PH10) (However, the developer was adjusted to PH10 with an aqueous sodium hydroxide solution and dilute sulfuric acid.) [Fixer] Hypo 240gr Sodium sulfite 10gr Sodium hydrogen sulfite 25gr Add pure water to make 1.0. The types of compounds used as developing agents in the above developer and the results of sensitometry during the development process are shown in Table 1 below.

[Example 2]

Photographic emulsions consisting of copper bromide fine grain crystals containing silver bromide were prepared using the three types of solutions shown below. [Solution 4] Ose -in gelatin pure water 16GR 800ml [solution 5] KBR L -ascorbic acid pure water 128.5GR 78.5GR 800ml [solution 6] CU (No ₃ ) ₂ 3H ₂ O AGNO ₃ Pure water 144.6GR 10.2GR 990ml [ Keeping the temperature of Solution 4 at 45°C, start adding [Solution-5] and [Solution-6] at the same time using the double jet method while stirring.
The entire amount was added over 20 minutes at a rate of 40 ml/min, while [Solution-6] was added at a rate of 45 ml/min over 22 minutes. Furthermore, the temperature during physical ripening was maintained at 45°C. After adding both [Solution-5] and [Solution-6], add another 10
After physical ripening for a minute, washing with water and desalting were performed in the same manner as in Example-1. After washing with water and desalting, an aqueous ossein/gelatin solution (containing 50 g of gelatin) was added, stirring was continued for 30 minutes at 40°C to redisperse the mixture, and the total volume was adjusted to 900 ml with distilled water. A hardener and a surfactant (coating aid) are added to the emulsion.
was added, coated on a polyethylene terephthalate film support, and dried at 60° C. for 30 minutes to produce a photosensitive material-B to be used in the development of the present invention. The thickness of the emulsion layer after drying was 4 μm. Note that the amount of cuprous halide contained in this photosensitive material is
When measured using the wire method, it was calculated as 32mg/metal copper.
It was ^100cm2 . Next, the photosensitive material was closely attached to an optical wedge (optical density step 0.1) using a light source having ultraviolet rays in the range of 260 to 420 μ, and was exposed to light of 10 ⁴ erg/cm ² through this. Thereafter, development was carried out at 25° C. for 4 minutes using a developer having the same composition as that used in the above examples and containing the α-amino acids shown in the table below. The types of compounds used as developing agents in the above developer and the results of sensitometry after development are shown in Table 2 below.

【table】

[Comparative example 1]

Regarding the photosensitive materials A and B in the above examples, the photosensitive material A was immersed in the following developer at 20° C. for 30 seconds in a wet state, and the photosensitive material B was in a dry state in the same manner as described above. An optical wedge (optical density step) using a light source with 420 mμ ultraviolet light
0.1), and exposure at 10 ⁴ erg/cm ² was performed through this. Thereafter, development was carried out at 20° C. for 1 minute using the developer shown below, followed by fixing using the fixer used in Example (1), followed by washing with water and drying. [Developer] Triethylenetetraamine 0.25mol Distilled water 1.0 (however, the developer is adjusted to pH 10.0 with dilute sulfuric acid) The results of sensitometry after development are shown in the table below. From this result, images obtained with developing solutions other than those of the present invention have a high fog density, a low maximum blackening density, a low contrast, and a low contrast in both the photosensitive materials (A) and (B). It can be seen that this is not a usable image.

[Example 3]

Cuprous oxide was prepared using a solution with the following composition. (Solution 1) Cuprous chloride Sodium chloride pure water 10gr 50gr 250ml (Solution 2) Potassium/sodium tartrate Sodium hydroxide pure water 10gr 10gr 150ml (Solution-2) While keeping the liquid temperature at 40℃ and stirring,
(Solution-1) is added. (Solution-1) was added over about 20 minutes, and after the addition was completed, stirring was continued for an additional 30 minutes. After the reaction, leave to stand to precipitate cuprous oxide, decant the supernatant, add 500 ml of 1% potassium/sodium tartrate aqueous solution, stir, and let stand again to precipitate coarse crystals. The clear liquid was decanted, washed with 500 ml of pure water, left to stand to settle coarse crystals, and the supernatant liquid was decanted. Finally, it was washed with acetone and dried at 45 to 50°C for 20 minutes. The cuprous oxide obtained by this method was coarse crystals with a particle size of 100μ or more. 12.5 grams of the crystals were pulverized in a ball mill for 5 hours, and 100 ml of a 5% aqueous gelatin solution was added, followed by pulverization and dispersion at 45° C. for 1 hour. The dispersion was adjusted so that the gelatin/Cu ₂ O ratio was 1/1, and a hardening agent and a hardening agent were added to the dispersion.
and surfactant (coating aid), total amount
Finished to 150ml, coated on a polyethylene terephthalate film support to a wet film thickness of 43μ, and heated at 60°C.
The material was dried for 30 minutes to produce a photosensitive material (C) to be subjected to the development of the present invention. The amount of cuprous oxide contained in this photosensitive material was measured using a fluorescent X-ray method and was found to be 33 mg/100 cm ² in terms of metallic copper. Next, the above-mentioned photosensitive material was heated at 20°C for 30 minutes using a developer having the composition shown below and using the compounds listed in the table below as a developing agent.
After immersion for seconds, in a wet state, a light source with ultraviolet rays in the range of 260 to 420 mμ is used to closely contact an optical wedge (optical density step 0.1) and pass through it.
An exposure of 10 ⁵ erg/cm ² was given. After that, it was developed with the same developer at 25℃ for 3 minutes, and then 10%
After being immersed in a KBr aqueous solution for 2 minutes, a fixing process was performed for 5 minutes or more using a fixing solution having the following composition. Further, washing and drying treatment was performed. [Developer] Amino acid 0.13mol Borax 2.62×10 ^-2 mol Pure water 1000ml (PH10) (However, the developer was adjusted to PH10 with sodium hydroxide or dilute sulfuric acid.) [Fixer] Hypo 240gr Sodium sulfite 10gr Sodium bisulfite 25g Add pure water to 1000ml The compound as a developing agent and the results of sensitometry after development are shown in Table 4 below.

[Comparative example 2]

The photosensitive material (C) described in the above example was mixed with 0.001NH ₂ SO ₄
Immerse it in an aqueous solution at 20°C for 5 seconds, and in a wet state use a light source with ultraviolet radiation of 260 to ⁴²⁰ mμ in the ^same way as in the previous method. I went. after that
After developing with a 0.01NH ₂ SO ₄ aqueous solution for 20 to 90 seconds, a fixing process was performed using the fixing method shown in Example 3. The results of sensitometry after development are shown in Table 5 below.

[Table] As is clear from the above table, when the cuprous oxide photosensitive material described in Example 3 was developed with a developer not according to the present invention, even if the development time was extended, the lowest density and the highest density remained. It was not possible to obtain the excellent image characteristics shown in Table 4 above in terms of both density and contrast.

Claims (1)

[Claims] 1 Photosensitive copper halide (1) or photosensitive copper oxide
An image forming method in which a photosensitive material having a layer in which (1) is dispersed in a binder or a layer consisting essentially of photosensitive copper oxide (1) on a support is imagewise exposed and then developed. Then, the following general formula (), ()
An image forming method comprising developing with a solution containing a compound represented by () or () to form a copper image. General formula [formula] [formula] [In the formula, R ₁ is an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.
4 aminoalkyl group, hydroxyaminoalkyl group having 1 to 4 carbon atoms, -(CH ₂ ) _o COOH, -(CH ₂ ) _o
CONH (where n represents an integer from 1 to 4),
[Formula] [Formula] (where m represents an integer from 1 to 3), -(CH ₂ ) _o NHCONH ₂ (however, n represents an integer from 1 to 4),
[Formula] (where q represents an integer of 1 or 2),
[Formula] (where n represents an integer from 1 to 4), [Formula] or [Formula] R ₂ is -OM (however, M represents a hydrogen atom or an alkali metal atom), -NH ₂ , or -NHR ₅ (However, R ₅ is an alkyl group having 1 to 6 carbon atoms,
4); R ₃ and R ₄ may be the same or different;
each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms,
[Formula] (where l represents an integer from 0 to 4), -CO(CH ₂ ) _l CH ₃ (however, l represents an integer from 0 to 4) or -CO(CH ₂ ) _o NH ₂ (how n is 1
~4); Y is −CH ₂ CHR ₆ CH ₂ −
(However, R ₆ represents a hydrogen atom or a hydroxyl group); Z represents -(CH ₂ ) _p - (However, p represents an integer from 4 to 6). ]