JPS63147167A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To obtain a stable positive color image by subjecting a photosensitive material to a fogging process in the presence of specific compds. at the time of developing said material while subjecting the same to the fogging process. CONSTITUTION:The photosensitive material is subjected to the fogging process in the presence of the compds. expressed by formula I, II or III in an image forming method to obtain the direct positive color image by developing the material while subjecting the same to the fogging process. In formula I, R1-R5 respectively denote a hydrogen atom, alkyl group of 1-4C, aryl group or hydroxyl group. In formula II, R6 denotes a hydrogen atom or alkyl group of 1-6C, R7, R8 denote a hydrogen atom, alkyl group of 1-2C, alkoxy group or halogen atom, etc. In formula III, R9, R10, R12, R13 respectively denote alkyl group of 1-4C, R11 denotes a hydrogen atom, alkyl group, etc., of respectively 1-2C. The fogging nuclei on the surface is thereby stabilized and the density of the positive image is improved. The need for large labor and cost for a non- polluting treatment of a waste processing liquid is thus eliminated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for forming a direct positive color image, and more specifically, an image forming method that can stably obtain an image using a direct positive silver halide color photographic light-sensitive material. Regarding.

[Background of the invention]

In recent years, positive images from printed manuscripts, versatile films, etc. are used as originals, and internal latent image type silver halide photographic light-sensitive materials are made using copying machines! After lithography, it is diluted in a color developing solution and developed, making it possible to obtain a printed image directly on color photographic paper or color film. Copy machines were installed and it became possible to copy originals on the spot.

Processing waste liquid from silver halide photographic materials (hereinafter referred to as "photosensitive materials") including the internal latent image type photographic materials mentioned above is
After being rendered harmless, they are disposed of, but this requires a great deal of effort and expense. Among them, solvents such as benol alcohol (color development accelerator) with 1ogP of 0.4 or more in color developing solutions have high D (biological oxygen demand) and C0D (chemical oxygen demand), and are a major problem. It becomes.

Various attempts have been made to reduce or eliminate the use of benzyl alcohol; however, in this case, the oxidized color developing agent generated in the development reaction is more likely to be absorbed by the sulfite ions (color developing agent) in the developer solution than to undergo a coupling reaction with the color former. (antioxidants), resulting in a decrease in image density.

One effective way to counter this is to reduce the sulfite ion concentration to increase the coupling reaction, but when an internal latent image type direct positive photosensitive material is developed with a color developer with a low sulfite ion concentration, Positive image density varies greatly due to various factors.

In the case of fogging with light, changes in illuminance, such as a decrease in the amount of exposure to the photosensitive surface due to a filter effect due to deterioration of the light source or oxidation coloring of the developer, and in the case of fogging with a fogging agent, air oxidation The density of the positive image formed is markedly reduced due to a decrease in the ability of the fogging agent.

Regarding the relationship between fogging and positive image formation in internal latent image type photosensitive materials, see, for example, "The Theory of the 7 Autographic Processes J" by Mies and Nohems.
This can be understood to some extent by the ``desensitizing effect due to internal latent images'' as discussed in ``Densitizing Effects Due to Internal Latent Images'', 3rd Edition, page 161. In other words, the surface sensitivity is reduced by a so-called negative internal latent image formed inside the silver halide grains in response to the initial image exposure. Furthermore, it is believed that a fogging process forms fogging nuclei in accordance with the surface sensitivity, and then a positive image is formed in the unexposed areas of the image by normal development.

In order to improve the drawback that positive images tend to fluctuate due to fluctuation factors during fogging when processed with a color developing solution having a low sulfite ion concentration, silver halide was used as described in U.S. Pat. No. 3,761.276. Although there is a method for improving the positive image density by stabilizing fogging nuclei on the surface by subjecting the particle surface to some degree of chemical formation, sufficiently satisfactory results have not been obtained.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and the first object of the present invention is to provide an image forming method capable of obtaining a stable positive color image (↑) using an internal latent image type direct positive color photosensitive material. The goal is to provide the following.

A second object of the present invention is to provide an image forming method using an internal latent image type direct positive photosensitive material, which can be processed with a processing liquid that has a low pollution load of waste liquid.

[Structure of the invention]

The above object of the present invention is to produce a direct positive color light-sensitive material containing internal latent image type silver halide grains whose front surfaces are not fogged in advance and a coloring agent, by using a solvent having a log P of 0.4 or more and a solvent of 1 g/l or less. and/or after fogging treatment in a color developer having a composition with a low sulfite ion concentration.
Alternatively, in an image forming method in which a positive color image is obtained directly by performing a development process while performing a fogging process, the ζ-curing process is performed in the presence of a compound represented by the following general formula (1), CII) or [■]. This was achieved by giving.

General formula CI) In the formula, R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and R2, R1, R4 and R1
each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group or a hydroxyl group.

General formula (I [] represents.R
8 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group, or a 210 dene atom.

Further, R6 and R7 may form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded, and the heterocyclic nucleus may contain an oxygen atom.

-, the following is a blank general formula (III) R13 In the formula, R5, R10% R12 and R13 each represent an alkyl group or an aralkyl group having 1 to 4 carbon atoms,
R represents a hydrogen atom, an alkyl group or alkoxy group having 1 to 2 carbon atoms, or a halogen atom, respectively.

Further, R9 and R1° and R1□ and R1ff may each form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded, and the heterocyclic nucleus may contain an oxygen atom.

The present invention will be explained in more detail below.

The compound represented by the general formula CI) is a 3-pyrazolidone derivative. In the formula, R,, R,, R3, R, or R
The alkyl group having 1 to 4 carbon atoms represented by 9 may be substituted, and preferred substituents include a halogen atom,
Examples include hydroxyl, carboxyl, and amine 7 groups. The aryl group (for example, phenyl, naphthyl group, etc.) represented by R,, R2, R3, R, or R5 may also be substituted, and the substituent may be a halogen atom, alkyl, alkoxy, alkylami/, acylami 7 group, etc. can be mentioned.

The compounds represented by the general formula (1) include the following.

(Exemplary compound) 1-phenyl-3-pyrazolidone, 1-p-)dyl-3
-pyrazolidone, 5-phenyl-3-pyrazolidone, 5
-Methyl-3-pyrazolidone, 1-p-chlorophenyl-3-pyrazolidone, 1-phenyl-5-phenyl-3
-Pyrazolidone, 1-+a-) Zyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-
p-) Zyl-5-phenyl-3-pyrazolidone, 1-p
-methoxyphenyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-
Acetyl-4,4-methyl-3-pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-aminophenyl-4-methyl-4-propyl-3-
Pyrazolidone, 1-o-chlorophenyl-4-methyl-
4-ethyl-3-pyrazolidone, 1-(p-β-hydroxyethyl 7enyl)-4,4-fusityl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1- p-) True 4,4-dimethyl-3-pyrazolidone, 1-(7-hydroxy-2-
(su7tyl)-4-methyl-4-11-propyl-3-pyrazolidone, 1-p diphenyl-4,4-dimethyl-3
-pyrazolidone, 1-(p-β-hydroxyethyl 7
enyl)-3-pyrazolidone, 1-0-tolyl-3-pyrazolidone, 1-o-)lyl-4,4-tumethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 4-hydroxy-4-methyl-1-phenyl-
3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4,4-nohydroxymethyl-1-phenyl-3-pyrazolidone.

The compound represented by the general formula (n) is a p-7 mi/phenol derivative. In the formula, the number of carbon atoms represented by R6 is 1
Examples of the alkyl group of -6 include methyl, ethyl, propyl, butyl, hexyl, and the like. Number of carbon atoms optionally substituted with a hydroxyl group represented by R7: 1
Examples of the alkyl group of ~2 include methyl, ethyl, and 2-hydroxyethyl groups. The heterocycle formed by R1, R, and a nitrogen atom is preferably a 5- or 6-shell ring, and examples include pyrrolinone, piperidine, piperazine, and morpholine rings.

The compounds represented by the general formula (If) include the following.

(Exemplary compounds) p-amino7ethyl, N-methyl-p-7mi/7eth/
-ru, 4-hydroxy-3-methyl-N, N-diethylaniline, 4-hydroxy-3-methyl-N-ethyl-
N-(β-hydroxyethyl)aniline, 4-hydroxy-3-methyl-N, N-dimethylaniline, 4-hydroxy-3-methyl-N-butyl-N-(β-hydroxyethyl)aniline, 4-hydroxy -3-methyl-N
-hexyl-N-(β-hydroxyethyl)aniline,
4-hydroxy-3-methoxy-N, N-diethylaniline, N-(4-hydroxy-3-methylphenyl)pyrrolidine, N-(4-hydroxy-3-methylphenyl)piperinone, 4-hydroxy-3- (β-hydroxyethoxy)-N,N-diethylaniline, N-(4-hydroxyethyl)piperazine, N-(4-hydroxyphenyl)morpholine.

The compound represented by the general formula CI) is a p-7 22-diamine derivative. In the formula, the alkyl group having 1 to 4 carbon atoms represented by R1, R1°, R12 or R13 may have a substituent, and the substituent is one of the above general formula (I).
The substituents for the alkyl group explained in R1 to R6 can be mentioned. R,,R,. , R12 or R23
The aralkyl group represented by may be substituted with an alkyl group having 1 to 4 carbon atoms. R9 and RIG or R1□
Examples of the heterocycle formed by and R1) together with a nitrogen atom include the same ring as the heterocycle formed by R6, R7 and a nitrogen atom in the general formula [I[).

The compounds represented by the general formula (I[I) include the following.

(Exemplary compounds) N, N, N', N'-tetramethyl-p-phenylenediamine, N, tonomethyl-p, N'-diethyl-p
-phenylenediamine, N,N,N',N'-tetraethyl-p-phenylenediamine, N,N-dimethyl-N'-methyl-N'-ethyl-p-phenylenediamine, N-methyl-N-(β -methoxyethyl)-3-methyl-4-tumethylami/aniline, N-(4-dimethylami/phenyl)morpholine, N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-4-dimethylami/aniline, N,N-tmethyl-3-methoxy-4-tmethylamino/aniline, N-(4-tmethylamino/phenyl)piperazine, N-(4-tmethylamino/phenyl)piperazine, methylaminophenyl)pyrrolidine, N,N-dimethyl-3-9 flow 4-dimethylfuminofuniline.

In the present invention, the general formula (1) (Il
) or (I [[) in the presence of a compound represented by [], selectively applied only to the surface of unexposed silver halide grains under relatively low illuminance in a limited range and under conditions with little illuminance failure due to light fogging. The entire surface is exposed to light in order to form a nucleus, but by covering it with a preservative and color development processing, it is clearly stable against changes in illuminance during full exposure and fluctuations in fogging agent concentration. We have discovered that it is possible to obtain a positive color image, and we have developed a commonly known method in which only a black and white developer or only a color developer is present, and the entire surface is exposed to light to obtain a black and white or color image. are clearly distinguished.

In addition, after imagewise exposure, silver is developed, a latent image is formed by reversal exposure on the surface or inside of the remaining undeveloped silver halide grains, and color development is performed to obtain a color image. Both processes are essentially different.

It is preferable to carry out the entire surface exposure at the beginning of development in terms of shortening the development time. In this case, it is advantageous to start the exposure after the developer has sufficiently penetrated the emulsion layer.

In the present invention, general formula (1), (It) or [I[
The compound shown in 1) may be contained in the photosensitive material, added to the prebath, or contained in the color developing solution. do not have. If it is added to a photosensitive material, it may cause problems such as the influence on the storage stability of the photosensitive material, so it is preferable to add it to the prebath or color developer. More preferably, it is added to a color developing solution.

In order to incorporate the compound represented by the general formula [I], [■] or [■] into the light-sensitive material, various methods known in the art can be employed. The amount added is 0.05 to 50 g per mole of silver halide, preferably [
2 is 0.1-10g. In addition, general formula [I], [
(2)] or (lI[]) When the compound is contained in a bath or color developing solution for impregnating a light-sensitive material, the amount to be added is 101 g to 10, 7'z.

Preferably 20mg to 3g7#! It is. Also, a compound of general formula CI), a compound of general formula [■] and a compound of general formula [■]
Two or more of these compounds may be used in combination.

The color developer used in the present invention has a log P of 0.4.
Is the content of the solvent above II? 71 or less and has a low concentration of sulfite ions.

The above log P is the partition coefficient P of n-oct/-L/water
This is the value obtained from The P value can be determined using the following formula.

The logarithm of the P value thus determined is the log P value, and this value has been widely used in the field of agrochemicals and medicines as a measure of fat solubility. The logP value is [Chemical Review+
) It can also be known from the logP oct in the table described in J, 1971, Vol. 71, No. 6, pp. 555-613. For example, Ecochemistry, Vol. 6, 3-
Although it can be determined theoretically by the calculation method described on page 11, it is preferable to use actually measured values, and particularly preferably to use values measured using n-octanol.

Solvents with a logP of 0.4 or more that are not preferably added to the developer used in the present invention include aliphatic alcohols, aliphatic glycol ethers, alicyclic alcohols, and aromatic alcohols. It has 5 to 20 atoms.

As a specific example, benol alcohol Nog P 1.10
0-Hydroxybennol alcohol #0.73 cyclohex/-l 〃1.232-pennoloxyeth/-l // 0.41 anisyl alcohol log P O, 701-penta/
-ru 〃0.4 or more phenylethyl alcohol // 1,36p-) Ril Calbi/
-le // 1.367 e7-le
Examples include p-hydroxybennoralcohol of 0.4 or more, benzylamine of 0.4 or more, noethylene glycol mo7-butyl ether of 0.4 or more, and the like.

As mentioned above, the solvent is a compound that promotes the coupling reaction between the oxidized color developing agent and the coupler of the light-sensitive material, and by reducing its content to a low concentration of 1 g/l or less, it is possible to reduce the Even when the color developer is discarded, the BOD and COO values can be kept low, which is effective in terms of pollution control. Furthermore, by lowering the concentration of sulfite ion as a preservative, the reaction with the solvent is controlled and the coupling reaction in color development processing is enhanced.

In addition, in the present invention, the sulfite ion concentration is low concentration.
The concentration is preferably 2×10 −2 mol or less per 11 color developer, more preferably 1×10 −2 mol/1.

As mentioned above, since the coupling reaction is effectively carried out by reducing the sulfite ion concentration, the color image developed by the color developing solution has a high maximum density (and a good image can be obtained).

The illuminance for full-surface exposure, that is, light fogging in the present invention, is preferably an illuminance that does not cause illuminance failure during light fogging, and varies depending on the photosensitive material, but is generally 0.01 to 2000 lux, preferably 0.05 to 30 lux, and more preferably can use light of 0.1 to 5 lux. Adjustment of the light power pre-illuminance can be done by changing the luminous intensity of the light source, by reducing the light using various filters, by adjusting the distance between the light-sensitive material and the light source, and by adjusting the angle between the light-sensitive material and the light source. . In addition, in order to shorten the exposure time,
It is also possible to adopt a method of fogging with weak light at the beginning of exposure, and then fogging with stronger light.

In the present invention, as a light source for light (J'), at least one light source within the sensitivity wavelength of the photosensitive material may be used, but as a light source for color photosensitive materials, it is preferable to use
It is preferable to use at least one light source having a wide spectral distribution over the range of 700 nI11 to 700 nI11, and a fluorescent lamp with high color rendering properties as described in JP-A-56-17350 may also be used. Furthermore, a combination of two or more types of light sources with different emission distributions and color temperatures may be used, and various filters such as color temperature conversion filters may be used.

Examples of the gauging agent used in the present invention include U.S. Pat.
563,785, hydranones described in 2,588,982, or U.S. Pat. No. 3,227,5
Hydrazide or hydrazone compounds described in U.S. Pat. No. 52; still U.S. Pat.
No. 479, No. 3,719.494, No. 3,734.7
Heterocyclic quaternary nitrogen salt compounds described in US Pat. No. 38 and US Pat. No. 3,759,901; furthermore, US Pat.
Examples include compounds having a TIJ1 group attached to the silver halide surface, such as the acylhydrano/phenylthioureas described in No. 25. Moreover, these fogging agents can also be used in combination. For example, RD 15162 describes the use of a non-adsorbent fogging agent in combination with an adsorption fogging agent, and this combination technique is also effective in the present invention.

Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydranone hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydrazine, 1-7 cetyl-2-"yxylhydrazine, 1-7 cetyl-2-(4-7 cetylhydrazine) amidophenyl)
Hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1
- hydranone compounds such as methylsulfonyl-2-(3-phenylsulfonamide 7enyl)hydranone and formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide)', 3
-(2-formylethyl)-2-7'-benzothiazolium bromide, 3-(2-7cetylethyl)-2-
Benzylbenzoselenazolium bromide, 3-(2-acetylethyl)-2-benzyl-5-phenylbenzoxacilium bromide, 2-methyl-3-[3-(phenylhydrazino)propyl 1benzothiazo Rium bromide, 2-methyl-3[3-(p-)lylhydrazi7)propyl 1-benzothiazolium bromide, 2-methyl-3
-[3-(p-sulfophenylhydrazino)propyl 1
Benzothiazolium bromide, 2-methyl-3[3(p
-sulfophenylhydrazino)pentyl]penzothiazolium iodide, 1,2-nohydro3-methyl-4-
phenylpyrid)' [2,1-bl benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2t1-bl -5-phenylbenzoxacilium bromide, 4.4'-ethylene Bis(1,2-dihydro-3-methylpyrido[2,1-bl benzothiazolium bromide), 1,2-novidro-3-methyl-4
-Phenylpyrido [N-substituted quaternary cycloammonium salt such as 2,1-bl benzoselenazolium bromide; 5
-(1-ethylna7)[1,2-b]thiazoline-
2-i') tenethylidene)-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)-2-thiohyguntoin, 5-(3-ethyl-2-penzothiazolinylidene) )-3-[4-(2-formylhydrano/)phenyl]rhodanine, 1-[4-(2-formylhydranoa)phenyl]-3-phenylthiourea, 1,3-bis(4-(2- Examples include formyl hydrazine) phenylcothiourea.

The color developing solution used in the present invention means a color developing solution that does not substantially contain a silver halide solvent, and examples of developers that can be used in the color developing solution include ordinary color developing agents. It will be done. Preferred color developing agents are aromatic primary amine compounds, typical examples of which include p-phenylenediamines represented by the following general formula (IV).

,'~ General formula [IY] with blank space below In the formula, R14 is an alkyl group having 1 to 6 carbon atoms, R15
is a hydroquinyl group, a methoxy group, a methoxyethoxy group,
Represents an alkyl group having 1 to 3 carbon atoms that may be substituted with a sulfo group, a methane sulfonylamine group, or the like.

R18 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 2 carbon atoms, or an alkoxy group, and the alkyl group may be substituted with a sulfo group, a methanesulfonylamide group, or the like.

For example, N,N-noethyl p-71 nylenediamine, 4
-ami7-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-7mi7-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline, 4- Amino-3-methyl-N,N-noethyl p
-Phenylenenoamine, 4-7mi/-3-methyl-
Examples include N-ethyl-N-β-methoxyethyl-p-phenylenenoamine.

These developers are included in the emulsion in advance, and
It is also possible to act on the silver halide during immersion in the H aqueous solution.

The amount of these aromatic #S primary amine compounds to be used varies depending on the type of light-sensitive material, but it is easy to determine experimentally, and is generally 0.0002 to 11 per developer.
It may be used within a range of 0.7 mol.

Furthermore, the color developer can contain specific antifoggants and development inhibitors, or these developer additives can be optionally incorporated into the constituent layers of the light-sensitive material. Generally useful antifoggants include heterocyclic thiones such as teFrazaindenes, benzotriazoles, pensiimiguzoles, benzothiazoles, benzoxazoles, 1-phenyl-5-mercaptotetrazole; Includes aromatic and aliphatic mercapto compounds.

Furthermore, various commonly added components may be added to the color developing solution. Examples include alkali agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali/group halides, water softeners, thickening agents, and development accelerators. The PU value of this color developer is usually 7 or more, most commonly about 9 to about 14.5, more preferably 10 to 14.

The working temperature of the color developing solution used in the present invention is usually 2.
0°C to 70'C1, preferably 30°C to 45°C.

Additives to the color developing agent used in the present invention include the above-mentioned anti-stinting agents, anti-surano agents, interlayer effect promoters, preservatives (eg, hydroxylamine hydrochloride), and the like. In addition, chelating agents include phosphates such as polyphosphates, aminopolycarboxylic acids such as nitrilotriacetic acid and 1-3-diamino-2-7' lovanoltetraacetic acid, ochynecarboxylic acids such as citric acid and gluconic acid, and 1-human 10 Examples include xyethylidene, 1,1-nophosphones, etc.9 It is also possible to use lithium sulfate in combination with a chelating agent, and these chelating agents may be combined.

The silver halide emulsion used in the light-sensitive material of the present invention forms a latent image mainly inside the silver halide grains without the grain surfaces being blurred in advance, and has most of the photosensitive nuclei inside the grains. It is an emulsion having halogenated root grains, and includes any silver halide, such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., preferably laminated type halogenated A core that is a silver particle and has silver chloride in the shell part/
Particularly preferred are shell particles.

In the internal latent image type silver halide grains of the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

The meaning that the grain surfaces are not prefogged means that the emulsion used in the present invention is coated on a transparent film support with a thickness of 35 m
This means that the density obtained when a test piece coated to give gAg/c+a2 is developed with the following surface developer A at 20°C for 10 minutes without exposure to light does not exceed 0.6, preferably 0.4. .

Surface developer A metric
2.
52L-7 Sulfic acid 103 Sodium metaborate (tetrahydrate) 35g Potassium bromide 1g Add water 11 Also according to the present invention /%
The silver lodenide emulsion provides sufficient density when the test piece prepared as described above is exposed and then developed with internal developer B having the following formulation.

Internal developer B metric
2.0
g Sodium sulfite (anhydrous) 9o, og
Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide
Add 0.5g water
12 More specifically, a portion of the specimen was exposed to a light intensity scale for a defined period of time up to about 1 second and developed for 10 minutes at 20'C' in Internal Developer B. exhibiting a maximum density of at least 5 times, preferably at least 10 times, that obtained if another portion of the specimen exposed under the same conditions was developed in surface developer A for 10 minutes at 20°C. It is something.

Specifically, for example, conversion type silver halide emulsions described in U.S. Pat. No. 2,592,250, U.S. Pat.
, 761,266 and 3,761,276, core/shell type silver halide emulsions doped with internal chemical sensitizing nuclei or polyvalent metal ions, JP-A-1988-8
524, 50-38525, and 53-2408, and other emulsions described in JP-A-52-156614 and JP-A-55-127549. I can do it.

The silver halide emulsion used in the present invention can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes used for supersensitization, such as internal latent image type silver halide emulsions and negative type silver halide emulsions, are also useful for the silver halide emulsions of the present invention. Regarding sensitizing dyes, please refer to Research Diskrono + - (Research
h Disclosure) No. 15162.

Silver halide emulsions keep surface sensitivity as low as possible,
In order to provide lower minimum concentrations and more stable properties, commonly used stabilizers such as compounds with azaindene rings and heterocyclic compounds with mercapto (typically 4-hydroxy-6- Examples include methyl-1,3,3a, 7-titrazaindene, 1-phenyl-5-mercaptotetrazole, and the like.

) can be included.

The silver halide emulsion contains antifoggants or stabilizers such as mercury compounds, triazole compounds,
Azaindene compounds, benzothiazolium compounds,
Zinc compounds and the like may be used.

Various photographic additives may optionally be added to the silver halide emulsion. Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid. copolymer with, styrene-maleic acid copolymer, styrene-
Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as maleic anhydride bar 7 alkyl ester co-mall are suitable, and as coating aids, for example, saponin, bo! Contains noethylene glycol lauryl ether, etc. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants,
Brighteners, development speed regulators, matting agents, etc. can be used.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to obtain an internal latent image type light-sensitive material.

The light-sensitive material of the present invention has at least one layer of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer for forming yellow, magenta, and cyan dye images, and the color former, that is, the coupler is a dye image of yellow, magenta, and cyan. As the coupler, an open-chain ketomethylene compound can be used, such as a benzoylacetanilide-based yellow coupler, a vivaylacetanilide-based yellow coupler, and a carbon atom at the coupling position that has a substituent that can be separated during the coupling reaction. Two-equivalent type yellow couplers can also be used advantageously. Furthermore, as mazene couplers, pyrazolone-based, pyrazolotriazole-based, virazolinobenzimigzole-based, and ingzolone-based compounds can be used. Furthermore, as cyan couplers, 7-enol and naphthol compounds can generally be used.

In addition, in order to prevent dye images from fading due to short-wavelength actinic rays, it is useful to use ultraviolet absorbers, such as thiazolidone, benzotriazole, acrylonitrile, and benzo-7-based compounds.
It is advantageous to use 201, 326, 327, and 328 (all manufactured by Ciba Geigy) alone or in combination.

Any support can be used for the photosensitive material used in the present invention, but typical supports include polyethylene terephthalate film, which is subbed-treated if necessary.
These include polycarbonate F film, polystyrene film, cellulose acetate film, baryta paper, polyethylene laminate paper, and the like.

In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or paints in the silver halide emulsion depending on the purpose. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders can be included depending on the purpose. In addition to gelatin, suitable binders include dextran, alginic acid, and hydrolyzed to an acetyl content of 19 to 20%. Cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. are included! i! It can be added to the constituent layers of the photosensitive material such as the L agent layer, intermediate layer, protective layer, filter layer, backing layer, etc., depending on the purpose.Furthermore, the hydrophilic binder can be added with appropriate plasticizing resistance and lubrication depending on the purpose. It is possible to contain agents, etc.

Also, the structure of photosensitive materials 7i! The layer can be hardened with any suitable hardener. These hardeners include:
Examples include chromium salts, norconium salts, aldehyde hardeners such as formaldehyde and mucohalogen acids, halotrianone hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners.

In addition, photosensitive materials include an emulsion layer, a filter layer, and a filter layer on a support.
It is possible to provide a large number of various photographic grooves 1'&layers such as an intermediate layer, a protective layer, a subbing layer, a backing layer, an antihalation layer, etc.

The present invention can be advantageously applied to ordinary multilayer direct positive color photosensitive materials that form dye images of basically three colors of yellow, magenta, and cyan as described above, but it is also applicable to direct positive color photosensitive materials with false colors and black color upon color development. The present invention can also be effectively applied to color light-sensitive materials containing compounds capable of forming images.

Also, the light of the present invention! ') The exposure method can also be used for direct positive color photosensitive materials in which the coupler and the color developing agent or color developing agent precursor are protected so as not to come into contact with each other when unexposed and are present in the same layer, and can come into contact with each other after exposure. In a direct positive color light-sensitive material, a color developing agent or a color developing agent precursor is contained in a layer that does not contain a coupler, and when an alkaline processing solution is permeated, the alkaline hydrolyzate of the color developing agent or color developing agent precursor is transferred. It can also be applied to color photosensitive materials that can come into contact with couplers.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 Equimolar silver nitrate aqueous solution and potassium bromide aqueous solution were mixed at 50'
Simultaneously added while controlling with C, average particle size 0.3
A silver bromide emulsion consisting of 14-sided tetradecahedral grains was obtained.

To this emulsion, a silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously added in an equimolar ratio to the core particles, and 0.55μ
Shoulder cubic laminated core/shell emulsion B was obtained.

A monochrome direct positive photosensitive material sample I was prepared by sequentially coating the following layers on a resin-coated paper support from the support side.

Layer 1...Yellow forming blue-sensitive silver halide emulsion layer α-(4-(1-bentrue-2-phenyl-3,5-nooxo-1.2.4-)riazolidinyl)]-]α-pivalyl as yellow coupler 2-chloro5-γ-(2
, 4-di-1amylphenoxy)butyramide] 120 g of aceto7nilide, 3.5 g of 2.5-no-1-octylhydroquinone.

Paraffin 200g, Tinuvin (Ciba Iggy Company H)
o.

g, dibutyl 7 thale) 100g, ethyl acetate 701
Mix and dissolve 11, add gelatin solution containing sodium dodecylbenzenesulfonate to disperse, and add to the internal latent image type silver chlorobromide emulsion B to give a silver amount of 400 g/x2 and a coupler amount of 400 x g/rx2. It was applied like this.

/! 2...Protective layer It was applied so that the amount of gelatin was 200zy/z2.

Note that layer 1 contained bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.

Sample (1) was divided into 50 equal parts, half of each was subjected to wedge exposure using a xenon lamp, and the following treatments 1.2.3.4 and 5 were performed.

[Processing 1] Light fog bath (20 seconds) - Color development (1 minute 40 seconds) - Bleach-fixing (1 minute) - Washing with water (1 minute) The processing temperature was 38°C in each step, and the composition of each layer was as follows. As shown.

[Light fogging bath and color developer]

Potassium carbonate 28.9g Potassium sulfite 1.58g Sodium pylbromide 0.26g Hydroxylamine sulfate 2.63 Diaminopropanol Tetraacetic acid
0.09g Sodium chloride 3.2゜Nitrilotamacetic acid 0.4g 4-amidium/
-3-Methyl-N-ethyl-N-(β-methanesulfonamidoethyl) aniline sulfate 5.0 g Add water to 11 (adjust to pH 10.30 with potassium hydroxide) equivalent to 0-2 mol/l of this lXl [Bleach-fix solution] Ammonium thiosulfate 110g Sodium bisulfite 10゜Iron ammonium ethylenenoaminetetraacetate 0g Ethylenediaminetetraacetic acid diammonium g Bisthiourea 2g Add water
11 (pH 6.5 with ammonia water)
The exposure conditions for light or ES') were as follows: a tungsten lamp was used as the light source, and the illuminance was varied in 5 steps using a neutral density filter to 0.2.0, respectively on the photosensitive surface.
4.0.8.1.2.1.6 lux.

Light fogging exposure is carried out for 10 seconds after immersing the sample in a light fogging bath for 10 seconds, then placing the sample horizontally after leaving the R+) bath so that the light hits the photosensitive surface vertically, and after exposure, placing it in a color developer. Soaked.

In treatment 1, the following compounds (^), (
100zl each of B), (C) or (D)? Treatments 2.3.4 and 5 were performed in the same manner as treatment 1 except that # was added.

(^) 1-phenyl-3-pyrazolidone (B)
4-H)'Waxymethyl-4-methyl-1-phenyl-
3-pyrazolidone (C) N-methyl-p-7 minophenol (D)
N,N,N',N'-Tetramethyl-p-phenylenenoamine The minimum and maximum densities of the images of each sample obtained by the above treatment are shown in Table 1.

Next, using the other half of Sample I in Processes 1.2.3.4 and 5, a pond with a concentration of potassium sulfite in the color developer of 2.5X 10-2 mol/1 was used under exactly the same conditions. As is clear from the results in Table 1, treatment 2 according to the present invention
．． For samples 3.4 and 5, it can be seen that positive yellow images that are stable against changes in illuminance due to light fogging exposure can be obtained. It is also seen that when the potassium sulfite concentration in the light fogging bath is high, the maximum concentration decreases.

Example-2 A sample similar to sample ① of Example-1 was prepared, and using this sample, in Processes 1.2.3.4 and 5 of Example-1,
Processes 11, 12, 13, 14 and 15 were carried out in the same manner except that the composition of the color developing solution was the same as the composition of the photofogging bath. A stable positive yellow image was obtained even with fluctuations.

In addition, in Processes 11.12.13.14 and 15, the ponds in which the potassium sulfite concentration in both the light bath and the color developing solution were set to 2.5X 10-2 mol/r were treated in the same manner as in Processes 16.17. 18, 19 and 20 were carried out, but a decrease in the maximum concentration was observed as in Example-1.

Example-3 In Example-1, the compounds (^), (B), and (C) added to the fogging bath were added to the protective layer of the direct positive photosensitive material sample (■).
Direct positive light-sensitive material samples n, m, rv and ■ were prepared in the same manner except that 73 of each of (D) and (D) were added per mole of silver chlorobromide.

Using Sample I of Example-1 and the above Samples 1 to V (1), the same treatments as Treatment 1 and Treatment 6 of Example-1 were performed, and the minimum and maximum concentrations were measured. The results are shown in Table-2. show.

-・, hereinafter nose 9 ・1, --2) As is clear from the results in Table 2, samples n, m, ■ and V to which the present invention was applied and treatment 1 (color developer with low sulfite ion concentration) When used in combination with the above method, a positive yellow image that is stable against fluctuations in illuminance due to light fogging exposure can be obtained. It is also seen that even for the samples (■ to V) containing the compounds of the present invention, the maximum density was reduced in Process 6 using a color developing solution with a high sulfite ion concentration.

Example 4 Silver bromide emulsion C consisting of tetradecahedral grains with a grain size of 0.3 μl was prepared by simultaneously adding and mixing equimolar silver nitrate aqueous solution and potassium bromide aqueous solution at 50°C, and emulsion C was used as a core particle. Further, an aqueous solution of silver nitrate and an aqueous solution containing equimolar amounts of potassium bromide and sodium chloride were added to obtain a cubic laminated core/shell emulsion having a grain size of 0.45 μm.

A positive sample (2) was prepared by directly applying the following layers onto a resin-coated paper support from the support side.

J'! ! II: Cyan-forming red-sensitive silver halide emulsion layer A sensitizing dye having the following structure was added to the emulsion for optical sensitization.

Separately, as a cyan coupler, 2,4-dichloro-3-methyl-6-[α-(2,4-cy-monoamylphenoxy)]
Butylamide]phenol was dissolved in dibutyl 7-thalerate and ethyl acetate, and dispersed in an aqueous gelatin solution to obtain an emulsified dispersion.

The coupler dispersion was added to the above-mentioned optically sensitized emulsion, mixed, a hardener was added, and the mixture was coated and dried to give a silver content of 500 B/z2.

Sample (1) was divided into 25 equal parts, subjected to wedge exposure through a yellow filter, and subjected to the following treatments 21, 22, 23, 24 and 25.

[Processing 21] After developing for 13 minutes at 38° C. with a color developing solution having the following composition, bleach-fix, wash with water and dry.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate 5.0 g Sodium sulfite (anhydrous) 0.63. Potassium carbonate 20g Potassium bromide 0.5g Benzyl alcohol 0.69 formyltolylhydrazine (
Fogging agent) Add the amount of water shown in Table 3 (adjust to pH 12.0 with potassium hydroxide), 5X10
- equivalent to 3 mol/1 In Process 21, the following compound (E) was added to the color developer,
The ponds to which 50 zg/l of each of (F), (G) or ()l) were added were subjected to treatments 22, 23, 24 and 25 similar to treatment 11.

(E) 1722-4,4-dimethyl-3-pyrazolidone (F) 4-hydroxy-3-methyl-N,N-noethylaniline (G) N-(4-hydroxyphenyl)morpholine (
H) N-(4-Tmethylaminophenyl)pyrrolidine The minimum and maximum densities of images of each sample obtained by the above treatment are listed in Table 3. -1, hereafter margin ゛-+' From the results in Table 3, it can be seen that in the samples to which the present invention is applied, stable positive images with little variation in maximum density can be obtained even if the fogging agent concentration varies.

Next, in processes 21.22.23.24 and 25,
The concentration of sulfite in the color developer is 3. OX
Treated in the same manner except that the concentration was changed to 10-2 mol/l 26.27
．． Nos. 28, 29 and 30 were carried out, but the maximum concentrations were clearly lower in both cases than in the corresponding cases 21, 22, 23, 24 and 25.

Claims (1)

[Scope of Claims] A direct positive silver halide color photographic light-sensitive material containing internal latent image type silver halide grains whose grain surfaces have not been fogged in advance and a coloring agent is prepared by using a solvent having a logP of 0.4 or more and 1
An image forming method in which a positive color image is directly obtained by developing in a color developing solution having a composition of g/l or less and a low sulfite ion concentration after fogging treatment and/or while fogging treatment is performed. In, the following general formula [
A method for forming a direct positive color image, which comprises performing a fogging treatment in the presence of a compound represented by [I], [II] or [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group,
and R_5 each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a hydroxyl group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. may be substituted with a hydroxyl group). R_8 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group, or a halogen atom. Also R_6
and R_7 may form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded, and the heterocyclic nucleus may contain an oxygen atom. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_9, R_1_0, R_1_2 and R_1
Each of _3 represents an alkyl group or an aralkyl group having 1 to 4 carbon atoms, and R_1_1 represents a hydrogen atom, an alkyl group or alkoxy group having 1 to 2 carbon atoms, or a halogen atom, respectively. Also R_9 and R_1_0 and R
_1_2 and R_1_3 may each form a nitrogen-containing heterocycle together with the nitrogen atom to which they are bonded, and the heterocyclic nucleus may contain an oxygen atom. ]