JP2005321691A - Processing composition for silver halide color photosensitive material having bleaching capability, and processing method for silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the processing composition for a silver halide color photosensitive material having high bleaching capability even under the condition of fast and low replenishing processing, and having the bleaching capability superior in a recoloring property and a desilvering property, and also to provide a processing method of a silver halide color photosensitive material. <P>SOLUTION: The processing composition for the silver halide color photosensitive material is provided which has the bleaching capability characterized by containing titanium compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a processing composition for a silver halide color photographic light-sensitive material having a novel bleaching ability and a method for processing a silver halide color photographic light-sensitive material.

  In general, a method of forming a dye image by processing a silver halide color photographic light-sensitive material (hereinafter also referred to as light-sensitive material, color paper, or color negative film) is performed with a color developer after imagewise exposure. Rinse through a desilvering step that includes two steps: a bleaching step in which silver particles contained in the photosensitive material are oxidized to silver ions, and a fixing step in which silver ions generated by the oxidation are dissolved and removed from the photosensitive material. Or it processes by the stabilization process for stabilizing a pigment | dye. In particular, in the processing of color paper, from the viewpoint of speeding up, the bleaching process and the fixing process are processed in the same bath as the bleach-fixing process.

  By the way, the photosensitive material is usually continuously processed (also called a running process) by an automatic developing machine provided at a developing station. In the development processing of such a photosensitive material, as a part of improving service to users, The development process is required to be returned to the user within the day when the request for development is received, and the development of a rapid processing technique is required at the same time. In addition, even ultra-rapid processing that returns several tens of minutes from the reception is required, and the development of rapid processing technology is increasingly required.

  Under such circumstances, Eastman Kodak Company has proposed rapid processing of color paper called process RA4 and rapid processing of color negative film called process C-41RA. More rapid processing than -41RA has been put into practical use, and there is an increasing demand for rapid processing.

  On the other hand, in recent years, low replenishment processing has been actively carried out to reduce the replenishment amount of processing liquids in order to reduce the cost of development processing agents or to reduce the amount of waste liquids that cost collection and processing, thereby reducing pollution. ing. However, if the processing time is significantly increased and processing is performed at a low replenishment rate, especially in laboratories with a large amount of light-sensitive material, oxidation of the bleaching solution cannot catch up and sufficient bleaching ability cannot be obtained. It turns out that a problem occurs.

  On the other hand, the bleach-fixing processing composition used in the bleach-fixing process mainly includes a bleaching agent and a fixing agent. Generally, the fixing agent has a reducing property, and both of them have no preservative. Is known to react easily and deactivate. Usually, sulfites are used as preservatives, but the preservatives decompose over a long period of time, and even when preservatives are present, there are few if they are concentrated to a high concentration. Since both of them react and lead to the result of impairing the original performance, the state (kit) supplied as a product is often designed as a two-part configuration of a bleaching part and a fixing part. . However, when handling multiple parts, the complexity of the user increases, and the problem is that the target replenishment concentration cannot be obtained due to mishandling during dissolution. A so-called single-part (one-part) configuration that can be used as a replenisher is desired.

  Various methods have been disclosed and proposed for making a part of a bleach-fixing processing composition (see, for example, Patent Documents 1 and 2). In Patent Document 1, mention is made of the stability of the processing solution at high temperature, the colorability of the container, and the bleaching stability after storage. On the other hand, Patent Document 2 mentions precipitation at low temperature, processing solution stability at high temperature, and bleaching stability at running processing. In particular, according to the technique described in Patent Document 2, even a one-part concentration kit has sufficient storage stability, and when used, the iron complex salt is changed to Fe (III) by air oxidation or addition of an oxidizing agent, Good bleaching ability is obtained.

However, it has been found that if the processing time is shortened and the replenishment is performed and the processing is performed under continuous processing conditions, air oxidation cannot catch up and a good bleaching ability cannot be obtained even in a laboratory other than a large amount of processing. . A bleach-fixing solution in which the pH, the amount of iron complex, the amount of thiosulfate, and the composition ratio of Fe (II) are specified has been proposed (for example, see Patent Document 3). However, the technique proposed in Patent Document 3 has a problem that leads to cost increase because the preservative is deactivated by aeration and a special device is used.
JP 2000-98553 A JP 2002-169253 A JP 2003-156824 A

  The present invention has been made in view of the above problems, and its object is to provide a halogen having a high bleaching ability and a bleaching ability having excellent recoloring and desilvering properties even under rapid and low replenishment processing conditions. The present invention provides a processing composition for a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A processing composition for silver halide color photographic light-sensitive materials having bleaching ability, comprising a titanium compound.

(Claim 2)
2. The processing composition for a silver halide color photographic light-sensitive material having bleaching ability according to claim 1, wherein the titanium compound is titanium oxide.

(Claim 3)
An iron complex salt is contained, and the titanium compound is contained in an amount of 2 × 10 ⁻⁵ mol% or more and 8 × 10 ⁻³ mol% or less with respect to the number of mols of iron ions of the iron complex salt. A processing composition for a silver halide color photographic light-sensitive material having the bleaching ability according to 1 or 2.

(Claim 4)
A bleach-fixing concentrated composition comprising an iron complex salt and a thiosulfate and comprising a one-part composition, wherein the ratio of Fe (II) value to the total iron ions of the iron complex salt is 50 mol% or more The processing composition for a silver halide color photographic material having bleaching ability according to any one of claims 1 to 3.

(Claim 5)
A processing method for a silver halide color photographic light-sensitive material, comprising processing using the processing composition for a silver halide color photographic light-sensitive material having bleaching ability according to any one of claims 1 to 4.

  According to the present invention, a processing composition for a silver halide color photographic light-sensitive material and a halogen having high bleaching ability and excellent bleaching ability and desilvering property even under rapid and low replenishment processing conditions. A method for processing a silver halide color photographic light-sensitive material can be provided.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the present inventor has obtained a bleaching ability-containing silver halide color photographic light-sensitive material-containing processing composition containing a titanium compound, so that even under rapid and low replenishment processing conditions. It has been found that a processing composition for a silver halide color photographic light-sensitive material having a high bleaching ability and a bleaching ability excellent in recoloring and desilvering properties can be realized, and as soon as the present invention has been achieved.

  Details of the present invention will be described below.

  The processing composition for a silver halide color photographic light-sensitive material having bleaching ability of the present invention (hereinafter also referred to as processing composition having bleaching ability) is a bleaching solution (bleaching processing composition), a bleach-fixing solution (bleach-fixing processing). Composition), and may be in any state of a tank solution (use solution) or replenisher used in the treatment, or a kit in the form of a product.

  The treatment composition having bleaching ability of the present invention is characterized by containing at least a titanium compound. In the present invention, by adding a titanium compound to a processing composition having bleaching ability, even if continuous processing is performed under rapid processing conditions without affecting other processing characteristics, As a result, it has a high bleaching ability and can be processed with excellent desilvering and recoloring properties.

  The titanium compound that can be used in the treatment composition having bleaching ability of the present invention is not particularly limited, and examples thereof include titanium oxide, potassium titanate, barium titanate, magnesium titanate, calcium titanate, strontium titanate, Titanium tetrachloride, titanium trichloride, titanium fluoride, titanium sulfate, titanyl sulfate, titanium nitrate, titanium oxysulfate, titanium oxychloride, tetraalkoxy titanium, potassium potassium oxalate dihydrate, sodium hexafluorotitanate, hexafluoro Potassium titanate, ammonium hexafluorotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetra-n-butyl titanate, di-n-butoxy bis (triethanolamine) titanate, dihydroxy bis (lactide acid) Titanate, di -i- propoxy bis (ethylacetoacetate) titanate, but di -i- propoxy bis (acetylacetone) titanate, and the like, among the above exemplified titanium compounds, it is particularly preferable to use titanium oxide.

  In the treatment composition having the bleaching ability of the present invention, the addition amount of the titanium compound according to the present invention is not particularly limited, but is preferably in the range of 0.1 to 50 mmol per liter of the treatment composition having the bleaching ability.

In the range specified above, not only the effect of the present invention is more remarkable, but also a stable treatment composition is obtained without causing precipitation or precipitation in the treatment composition.
Further, the treatment composition having the bleaching ability of the present invention contains the following iron complex salt as a bleaching main agent, and the titanium compound is contained in an amount of 2 × 10 ⁻⁵ mol% or more, 8 It is preferable to contain it at ^10-3 mol% or less. By making it the range prescribed | regulated above, the effect of this invention is more remarkable.

  Next, components of the treatment composition having the bleaching ability of the present invention will be described.

  The processing composition having bleaching ability of the present invention can contain any bleaching agent such as persulfate and hydrogen peroxide as a bleaching main agent, but the following general formulas [I], [II], [III] or The aminopolycarboxylic acid as shown in [IV], a previously complexed iron complex salt, or a ferric salt or a ferrous salt, and the aminopolycarboxylic acid were allowed to coexist and complexed in the liquid. It is a preferable form to contain an iron complex salt or the like.

  Examples of the ferric salt include, for example, ferric nitrate, ferric chloride, ferric bromide, iron (III) trisulfate (III) 3M1, and iron (III) sulfate M1 (where M1 is ammonium, potassium, sodium) More specifically, ferric nitrate, ferric chloride, ferric bromide, iron (III) trisulfate, iron (III) trisulfate, and the like. Examples include tripotassium, iron (III) trisulfate trisodium, potassium iron (III) sulfate, sodium iron (III) sulfate, and iron (III) ammonium sulfate. In addition, ferrous ammonium sulfate, ferrous sodium sulfate, ferrous ammonium sulfate, ferrous sodium sulfate, ferrous chloride, ferrous bromide, ferrous sulfate, acetic acid 1 iron, ferrous oxalate, iron oxide and the like.

  The aminopolycarboxylic acid represented by the general formula [I], [II], [III] or [IV] will be described below.

In the general formula [I], A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —COOM, or —PO ₃ M ₁ M ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal or other cation. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

In the above general formula [II], A ₁ ~A ₃ have the same meanings as those defined by the general formula [I], n represents an integer of 1-8. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, ethylene, propylene, butylene, pentamethylene, etc.). Examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group).

In the general formula [III], R ₁ represents a hydrogen atom or a hydroxyl group, n is 1 or 2, x is 2 or 3, y is 0 or 1, and the sum of x and y is always 3.

In the general formula [IV], A _{1 to} A ₄ are the same as defined in the general formula [I], and X is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms (for example, ethylene, Each group such as trimethylene and tetramethylene) or-(B ₁ O) _n -B _2- . B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms (for example, each group such as methylene, ethylene, trimethylene, etc.). n is an integer of 1 to 8, preferably 1 to 4.

  Preferred specific examples of the compound represented by the general formula [I] are shown below.

I-1: 1,3-propanediaminetetraacetic acid I-2: 2-hydroxy-1,3-propanediaminetetraacetic acid I-3: 2,3-propanediaminetetraacetic acid I-4: 1,4-butanediamine Tetraacetic acid I-5: 2-Methyl-1,3-propanediaminetetraacetic acid I-6: N- (2-hydroxyethyl) -1,3-propanediamine triacetic acid I-7: 1,3-propanediaminetetrakis Methylenephosphonic acid I-8: 2-hydroxy-1,3-propanediaminetetrakismethylenephosphonic acid I-9: 2,2-dimethyl-1,3-propanediaminetetraacetic acid I-10: 2,4-butanediaminetetra Acetic acid I-11: 2,4-pentanediaminetetraacetic acid I-12: 2-methyl-2,4-pentanediaminetetraacetic acid As iron complex salts of these compounds I-1 to I-12, Sodium salts of iron complex salt, potassium salt or ammonium salt can be used any.

  Specific examples of the compound represented by the general formula [II] are shown below.

  As the iron complex salts of these exemplified compounds II-1 to II-7, a sodium salt, potassium salt or ammonium salt of the iron complex salt of these compounds can be arbitrarily used.

Specific examples of the compound represented by the general formula [III] include
III-1: Nitrilomonopropionodiacetic acid
III-2: Examples include nitrilotriacetic acid, and sodium salts, potassium salts, ammonium salts, and the like can be arbitrarily used.

  Specific examples of the compound represented by the general formula [IV] are shown below, but the present invention is not limited to these exemplified compounds.

  As the iron complex salts of these exemplary compounds IV-1 to IV-17, a sodium salt, a potassium salt or an ammonium salt of the iron complex salt of these compounds can be arbitrarily used.

  The concentration of the iron complex salt in the treatment composition having bleaching ability of the present invention is suitably in the range of 0.003 to 0.10 mol / liter, preferably in the range of 0.02 to 0.50 mol / liter, More preferably, it is the range of 0.05-0.40 mol / liter.

  In the range specified above, not only an excellent bleaching ability is obtained, but also a stable treatment composition is obtained without precipitation of iron complex salts.

  The treatment composition having bleaching ability according to the present invention includes chloride, bromide, iodide as a rehalogenating agent for accelerating silver oxidation in addition to the above-described compound containing the iron complex salt as a bleaching agent. A halide such as is added. Moreover, you may add the organic ligand which forms a hardly soluble silver salt instead of a halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, potassium bromide, ammonium bromide, potassium chloride, and guanidine hydrochloride. As the corrosion inhibitor, nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate, or the like is used. The addition amount is preferably 0.01 to 2.0 mol / liter, more preferably 0.05 to 0.5 mol / liter. The bromide ion concentration in the bleaching solution of the present invention is preferably 1.8 mol / liter or less, more preferably in the range of 0.1 to 1.6 mol / liter. When the inorganic oxidizing agent as described above is used in combination, the bromide ion concentration is preferably in the range of 0.05 to 0.10 mol / liter. Bromide ions may be added to the bleach-fixing solution of the present invention, and the range of 1.0 mol / liter or less is preferred.

  In the present invention, ammonium ion, sodium ion, potassium ion, or the like can be used as a counter cation of bromide ion.

  In the bleaching treatment composition according to the present invention, the preferred pH is 3.0 to 7.0, and particularly preferably 3.5 to 6.5. On the other hand, in the bleach-fixing composition according to the present invention, the preferred pH is 3.0 to 8.0, more preferably 4.0 to 7.5. In the above pH range, not only high bleaching ability can be obtained, but also stain and the like are not generated, and excellent processing performance can be obtained.

  In order to adjust to the above pH range, a known organic acid can be used. In the present invention, the treatment composition having bleaching ability may contain 0.1 to 1.2 mol / liter of an organic acid having a pKa of 2.0 to 5.5.

  In the present invention, pKa represents a logarithmic value of the reciprocal of the acid dissociation constant, and shows a value obtained at an ionic strength of 0.1 mol / liter and 25 ° C. The organic acid having a pKa of 2.0 to 5.5 used in the present invention may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, if its pKa is in the above range, it can be used as a metal salt (for example, sodium or potassium salt) or an ammonium salt. Two or more organic acids having a pKa in the above range can be used in combination. Preferable specific examples of organic acids having a pKa of 2.0 to 5.5 used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid Aliphatic monobasic acids such as butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, etc. Amino acid compounds; benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, and aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxalo Aliphatic dibasic acids such as acetic acid, glutaric acid and adipic acid; aspartic acid, glutamic acid, cis Emissions, amino acid-based dibasic acids such as ascorbic acid; phthalic acid, and terephthalic acid, aromatic dibasic acids; can enumerate various organic acids such as polybasic acids such as citric acid. In the present invention, among these, glycolic acid, succinic acid and maleic acid are preferable because they have relatively little influence on the bleaching ability.

In the present invention, various bleaching accelerators can be added to the treatment composition having bleaching ability. Examples of such a bleach accelerator include, for example, US Pat. No. 3,893,858, German Patent 1,290,812, British Patent 1,138,842, 53-95630, Research Disclosure No. 17129 (July 1978), a compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A No. 50-140129, US Pat. No. 706,561, thiourea derivatives described in JP-A-58-16235, iodides described in German Patent No. 2,748,430, Japanese Patent Publication No. 45-8836 The polyamine compounds described in the publication can be used. Particularly preferred are mercapto compounds as described in GB 1138842.
Further, in the treatment composition having the bleaching ability of the present invention, it is preferable to use ammonium ions when considering the speed of treatment. On the other hand, when emphasizing environmental conservation, it substantially contains ammonium ions. Preferably not. In the present invention, “substantially free of ammonium ions” means that the ammonium ion concentration is 0.1 mol / liter or less, preferably 0.08 mol / liter or less, more preferably 0.01 mol. / Liter or less, particularly preferably represents a state in which none exists. In order to make the concentration of ammonium ions in the above range, alkali metal ions are preferable as alternative cation species, and sodium ions and potassium ions are particularly preferable. Specifically, sodium and potassium salts of aminopolycarboxylic acid iron complex salts as bleaching agents, potassium bromide and sodium bromide as rehalogenating agents in bleaching solutions, potassium nitrate and nitric acid as corrosion inhibitors Sodium etc. are mentioned. Examples of the alkaline agent used for pH adjustment include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like.

The replenishing amount of the processing composition having a bleaching ability is preferably 80 to 500 ml, more preferably 80 to 200 ml per 1 m ² of the light-sensitive material in the bleaching processing composition. The replenishing amount of the bleach-fixing composition is preferably 20 to 250 ml, more preferably 20 to 110 ml, still more preferably 30 to 100 ml per 1 m < ² > per photosensitive material. The lower the replenishment, the more remarkable the effect of the present invention.

  In the present invention, specific examples of the treatment step having bleaching ability include the following.

1) Bleaching-fixing 2) Bleaching fixing 3) Bleaching-washing-fixing 4) Bleaching-bleaching fixing 5) Bleaching-washing-bleaching fixing 6) Bleaching-bleaching fixing-fixing Each process may be divided into a plurality of baths if necessary, and may adopt a cascade system.

  In the present invention, when the processing composition having bleaching ability is a bleach-fixing processing composition, the time required for the step of deleting is preferably set within 90 seconds, particularly preferably 45 seconds, more preferably within 26 seconds. Thus, the effect of the invention is remarkably exhibited under rapid processing conditions.

  The time required for the above-mentioned process means the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. Or it refers to the time until the photosensitive material is immersed in the stabilization processing tank, and includes the crossover time. The crossover time is preferably 5 seconds or less, more preferably 3 seconds or less. The temperature of the treatment step is preferably 20 to 60 ° C, and preferably 25 to 60 ° C.

  In the present invention, when the treatment composition having bleaching ability is a bleaching treatment composition, the time required for the treatment step is preferably set within 2 minutes, more preferably within 45 seconds, and even more preferably within 26 seconds. Thus, the effect of the invention is remarkably exhibited under rapid processing conditions. The time required for the above-mentioned process means the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the processing tank, and includes the crossover time. The crossover time is preferably 5 seconds or less, more preferably 3 seconds or less.

  The temperature of the treatment step is preferably 20 to 60 ° C, and preferably 25 to 60 ° C.

  In the bleaching composition, aeration may be performed. Any means known in the art can be used for aeration. Regarding aeration, the items described in Eastman Kodak Co., Ltd., Z-121, Yuging Process C-41 3rd Edition (1982), BL-1 to BL-2 can be used. Further, in the treatment of the bleaching solution, it is preferable that the agitation is strengthened. For the implementation, it is described in JP-A-3-33847, page 8, upper right column, sixth line to lower left column, second line. The contents can be used as they are. Among these, a jet stirring method in which a bleaching solution is sprayed onto the emulsion surface of the light-sensitive material is particularly preferable. Moreover, although there is no restriction | limiting in particular in process temperature, Preferably it is 25-50 degreeC, Especially preferably, it is 35-45 degreeC. Moreover, when the processing liquid which has bleaching ability is a bleaching liquid, the overflow liquid after use for a process can be collect | recovered, a component can be added, a composition can be corrected, and it can reuse. Such a method of use is usually called reproduction, but such reproduction is also preferable in the present invention.

  In addition to the above, the methods described in “Basics of Photographic Engineering—Silver Salt Photography” (edited by the Japan Photography Society, published by Corona, published in 1979) can be used. Specifically, in addition to electrolytic regeneration, regeneration of bleaching solution with bromic acid, chlorous acid, bromine, bromine precursor, persulfate, hydrogen peroxide, catalytic hydrogen peroxide, bromous acid, ozone, etc. Include, but are not limited to, methods.

  Next, the fixing agent contained in the fixing solution (fixing processing composition) or the bleach-fixing processing composition according to the present invention will be described.

  Fixing agents include sodium thiosulfate, ammonium thiosulfate, ammonium thiosulfate, thiosulfate such as potassium thiosulfate, thiocyanate (rhodan salt) thiourea such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, A thioether or the like can be used. When thiosulfate is used alone as a fixing agent, it is preferably 0.3 to 3 mol, more preferably 0.5 to 2 mol per liter of the fixing processing composition or the bleach-fixing processing composition according to the present invention. When the thiocyanate is used alone, about 1 to 4 mol is preferable. In general, the amount of the fixing agent is preferably 0.3 to 5 moles, more preferably 0.5 to 3.5 moles per liter of the fixing processing composition or bleach-fixing processing composition, including the case where it is used in combination. That's fine. However, when used together, the total amount may be within the above range. In addition, examples of compounds other than thiocyanate that can be used in combination with thiosulfate include thiourea and thioether (for example, 3,6-dithia-1,8-octanediol).

  The fixing processing composition or the bleach-fixing processing composition according to the present invention may contain various other antifoaming agents or surfactants, organic solvents such as polyvinylpyrrolidone and methanol, or preservatives.

  Preservatives include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) and metabisulfites (eg, Sulfite ion releasing compounds such as potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, etc. Good. In that case, the amount of these compounds added is preferably about 0.02 to 0.8 mol / L in terms of sulfite ion or sulfinate ion.

  The pH of the fixing treatment composition is preferably 4 to 9, and more preferably 5.5 to 8. In the above pH range, not only excellent fixing ability is obtained, but also no odor is generated, and good processing performance is obtained.

In order to adjust to the said pH range, it is preferable to contain the compound whose pKa is the range of 6-9 as a buffering agent. As these compounds, imidazoles such as imidazole and 2-methyl-imidazole are preferable. These compounds are preferably no more than 10 moles, preferably 0.1-3 moles per liter of treatment composition. The replenishing amount of the fixing processing composition is preferably 3000 ml or less, more preferably 200 to 1000 ml or less per 1 m ² of the photosensitive material. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing composition for the purpose of stabilizing the solution.

  Further, the time required for the treatment step applicable to the treatment composition is preferably within 3 minutes, more preferably within 2 minutes. The time required for the processing step refers to the time from the immersion of the photosensitive material in the first tank to the exit of the final tank when the process has a plurality of tanks. It means the time until the photosensitive material is immersed in the stabilization or rinsing bath and includes the crossover time. The temperature of the treatment step is preferably 20 to 60 ° C, and preferably 25 to 60 ° C. The crossover time is preferably 5 seconds or less, more preferably 3 seconds or less.

Further, when the processing composition having bleaching ability of the present invention is a bleach-fixing composition, it is in the form of a bleach-fixing composition comprising a one-part composition of the above iron complex salt and thiosulfate from the viewpoint of handleability. preferable. The bleach-fixing composition comprising the one-part composition is particularly preferably a concentrated composition from the viewpoint of storage space, transportation and handling.
“Concentration rate” is usually used as a practical measure of the degree of concentration. The concentration ratio of the present invention is represented by the volume ratio of the treatment liquid completed when the treatment composition is diluted with water and a target replenisher is prepared to the original treatment composition.

  The concentrated treatment composition need not be in a homogeneous liquid phase, and can be prepared as a replenisher by diluting with water. Any of the slurry-like composition containing this may be sufficient. Further, the concentration rate is preferably 1.2 or more and 5.0 or less from the viewpoint that long-term stability can be obtained without deactivating the preservative in the concentrated composition state.

The bleach-fixing composition comprising the one-part composition exhibits the effects of the present invention remarkably when the Fe (II) value ratio is 50 mol% or more.
As a means for achieving the Fe (II) value ratio to 50 mol% or more, the aminopolycarboxylic ferric complex salt may be reduced with a reducing agent such as sodium dithionite. Moreover, you may achieve by adjusting the ratio of the ferrous salt of the said inorganic iron salt and a ferric salt.

Next, the packaging material filled with the processing composition having bleaching ability will be described. The packaging material for the treatment composition having bleaching ability according to the present invention is preferably a container having a low oxygen permeability such as 50 ml / (m ² · day · atm) or less, and the packaging material is any material such as paper or plastic. Although a material may be used, a plastic material is preferable. The oxygen permeability here is a value measured according to JIS 1707 according to a conventional method.

  Examples of the plastic material preferable as the packaging material used in the present invention include the following general packaging materials.

(Group)
A: Polyolefin resin B: Polyethylene-vinyl acetate copolymer resin C: Ethylene-vinyl alcohol copolymer resin D: Polyamide resin E: Ceramic F: Acrylonitrile resin G: Polyethylene terephthalate resin H: Polyvinylidene halide Resin I: Polyhalogenated vinyl resin The resin used for the polyolefin resin layer is preferably polyethylene, low density polyethylene (hereinafter abbreviated as LDPE), medium density polyethylene (hereinafter abbreviated as MDPE). And high density polyethylene (hereinafter abbreviated as HDPE) can be used. The HDPE preferably used in the present invention has a density of 0.941 to 0.969. LDPE is synthesized by a high pressure polymerization method, and its density is 0.910 to 0.925.

  As the container used in the present invention, HDPE having the above-mentioned density range is preferably used. Further, the melt index of the HDPE (measured at a temperature of 190 ° C. and an extrusion pressure of 2.16 kg by the method defined in ASTM D1238). ) Is 0.3 to 7.0 g / 10 min, preferably 0.3 to 5.0 g / 10 min. Within this range, it is stable as a container for a treatment composition having bleaching ability. Although the preferable thickness of the container in this invention changes with materials, Preferably it is 0.1-2.0 mm, Especially preferably, it is 0.3-1.5 mm, More preferably, it is 0.4-1.0 mm.

  As the polyamide-based resin, nylon is preferably used in terms of puncture strength and pinhole resistance, and the thickness is preferably 3 to 50 μm, more preferably 5 to 30 μm. In particular, stretched nylon is preferred from the object effect of the present invention. Ceramic is an inorganic substance mainly composed of silicon oxide, and may be coated on polyethylene or polyethylene phthalate in vacuum. Specific examples of these include GL type (ceramic vapor deposition film) manufactured by Toppan Printing Co., Ltd.

  Examples of the ethylene-vinyl alcohol copolymer resin include Kuraray manufactured by Kuraray Co., Ltd., Everfilm (EF-XL, EF-F, EF-K) and the like.

  In addition, examples of the halogen of the polyvinylidene halide resin and the polyvinyl halide resin include chlorine, fluorine, bromine, and the like, specifically, resins such as polyvinylidene chloride, polyvinylidene fluoride, and polyvinyl fluoride. .

  However, in the present invention, from the viewpoint of environmental suitability, generation of harmful gas is not preferred during the incineration treatment, and therefore, among the group, A to G are preferably used, and particularly preferably A to F.

  Each resin used in the present invention is one that satisfies the conditions of the present invention from those described in “Plastic Film” (published by Nikkan Kogyo Shimbun, Yoshihisa Takahashi, supplemented on December 20, 1976). be able to.

  These materials may be used by being molded alone, but a so-called multilayer film in which two or more kinds of materials are bonded together in a film form may be used. The shape of the wrapping material can take any configuration such as bottle type and pillow type.

  Although the production of the multilayer film is not particularly limited, for example, a method of adhering a film and a film with an adhesive, a method of adhering a film and a film with a molten resin, two or more kinds of resins together from a slit A so-called co-extrusion method and other commonly used film lamination methods can be used alone or in combination.

  Next, other processing steps constituting the development processing step using the processing composition having bleaching ability of the present invention will be described.

  First, the color development processing composition will be described.

  Preferred examples of the color developing agent used in the color developing composition according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. Is not to be done.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 14) N- (4-Amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 16) N- (4-Amino-3-methylphenyl) -3-pyrrolidinecarboxamide Of the above p-phenylenediamine derivatives, particularly preferred compound 5 ), 6), 7), 8) and 12), and among them, exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate, or the free base type as described above.

  The concentration of the aromatic primary amine developing agent in the working solution is added so as to be 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 to 40 mmol per liter of the developing solution. .

  An organic preservative may be added to the color developing composition. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being contained in the processing solution of the photosensitive material. That is, it is an organic compound having a function to prevent air oxidation of the color developing agent, such as hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, monoamines, diamines, polyamines. , Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  Further, as other preservatives, compounds represented by the following general formula (I) or (II) can also be contained.

In the general formula (I), L represents an alkylene group that may be substituted, A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, an amino group that may be alkyl-substituted, or an ammonio that may be alkyl-substituted. A carbamoyl group that may be alkyl-substituted, a sulfamoyl group that may be alkyl-substituted, a sulfonyl group that may be alkyl-substituted, a hydrogen atom, an alkoxyl group, or —O— (B—O) _n —R ′ , R and R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

In the general formula (I), L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, and an ammonio group that may be alkyl-substituted, and preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted, and a carboxyl group, a sulfo group, a hydroxyl group, Preferred examples include a phosphono group and an optionally substituted carbamoyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, or -O- ( B-O) _n- R 'and the like. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula (I), this invention is not limited to these compounds.

  Next, the compound represented by formula (II) will be described.

  In the general formula (II), R and R ′ each represents a saturated or unsaturated aliphatic hydrocarbon having 1 to 6 carbon atoms. In this case, these hydrocarbons may be substituted with a hydroxyl group, a carboxyl group, a sulfone group or the like. Moreover, you may contain bivalent coupling groups, such as a carbonyl group. n represents an integer of 4 to 50,000. s represents 0 or 1.

  If s takes 1, A is

Represents. R ″ represents an alkylene group having 2 to 8 carbon atoms or an alkanetriyl group which may be substituted with a hydroxyl group. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, q is 1. In the case of 1, B represents a polymer represented by the general formula (II), and the general formula (II) has a three-dimensional structure, and m represents an integer of 0 to 30.

  A compound represented by the general formula (II) in which s is 0, for example, poly (N-hydroxyalkyleneimine) can be easily synthesized by a known method. As a representative example, hydrogen peroxide described in “Journal of Chemical Society (J. Chem. Soc.), 75, 1009 (1899), J. Chem. Soc., 1963, 3144”, etc. An example is a method of synthesizing poly (alkyleneimine) by oxidizing a secondary amine using water. Since the crude poly (N-hydroxyalkyleneimine) synthesized by this method does not contain a component that affects photographic characteristics, it can be used as it is as a color developer composition without purification. Further, in combination with the reaction described in “Macromolecules”, 21, 1995 (1988) and the like, the primary amine which is the terminal group of poly (alkyleneimine) is changed to a secondary amine, thereby further improving the reaction. A method of synthesizing poly (N-hydroxyalkyleneimine) having excellent performance is also included. Examples of other methods include a synthesis method by reaction of hydroxylamine and dihalogenated alkylene, to which the method described in JP-A-3-259145 is applied.

  Hereinafter, typical examples of the compound represented by the general formula (II) are shown, but the present invention is not limited to these compounds.

  Other organic preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, triethanolamine and triiamine. Alkanolamines described in JP-A No. 54-3532, such as sopanolamine, polyethyleneimines described in JP-A-56-94349, US Pat. No. 3,746,544, etc. An aromatic polyhydroxy compound or the like may be contained as necessary.

The color developing composition of the organic preservative is preferably contained at 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less per liter. Further, the color developer may contain a small amount of sulfite ions or may not substantially contain sulfite ions depending on the type of the light-sensitive material, but in the present invention, it is preferable to contain a small amount of sulfite ions. Moreover, you may contain a small amount of hydroxylamine. Hydroxylamine (usually used in the form of hydrochloride or sulfate, but hereinafter abbreviated as salt) acts as a developer preservative in the same manner as sulfite ion, but at the same time, hydroxylamine itself has silver developing activity. For this reason, the photographic characteristics may be affected. Therefore, it is necessary to keep this addition amount small.

  The color developing composition may contain an aryl sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid, m-carboxybenzenesulfinic acid.

  The pH of the color developing composition is preferably 9.0 to 13.5, and the pH of the replenisher is preferably 9.0 to 13.5. For this reason, the color developing composition and the replenisher thereof may contain an alkali agent, a buffering agent and, if necessary, an acid so that the pH value can be maintained.

  Examples of the buffer for maintaining the pH include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, Guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate salt, 2-amino-2-methyl-1,3-provandiol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in a high pH range of pH 9.0 or higher, and even when added to a color developing composition, they adversely affect photographic performance ( This is a particularly preferable buffer because it is free from fog and the like and is inexpensive.

  Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroquinobenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  The amount of the buffer added is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol per liter for both the color developing composition and the replenisher.

  As the other color developing composition components, for example, calcium or magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color developing composition. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. The amount of these chelating agents may be sufficient to sequester the metal ions in the color developing composition. For example, 0. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developing composition. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44-30074 Quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182 and 4,230,796. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. The amine compounds described in the report or specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat. No. 3,128,183, JP-B-41-11431, JP-A-42-23883 and U.S. Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. The concentration of the color developing composition and its replenisher is preferably 0.001 to 0.2 mol per liter, and more preferably 0.01 to 0.05 mol.

  An optional antifoggant can be added to the color developing composition, if necessary, in addition to the halogen ions. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

Various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developing composition as necessary. The addition amount of the color developing composition and its replenisher is determined to be 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter.

  In the color developing composition, a fluorescent whitening agent can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available products can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And HakkolBRK are preferred.

  Other bis (triazinylamino) stilbene sulfonic acid compounds include compounds I-1 to I-48 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 and JP-A No. 2001-281823. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of 2001-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter for both the color developing composition and the replenisher.

The color development processing temperature that can be applied in the processing method of the present invention is 30 to 55 ° C., preferably 35 to 55 ° C., more preferably when the photosensitive material to be developed is color paper. Is 38-45 ° C. The color development processing time is 5 to 90 seconds, preferably 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. On the other hand, in the case of color development processing of a color negative film, the processing temperature is 20 to 55 ° C, preferably 30 to 55 ° C, more preferably 38 to 45 ° C. The color development processing time is 20 seconds to 6 minutes, and preferably 30 to 200 seconds. A smaller replenishing amount is preferred, but 100 to 800 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 200 to 500 ml, particularly preferably 250 to 400 ml. Both the color paper and the color negative film have a crossover time of 5 seconds or less, preferably 3 seconds or less. By setting the crossover time, there is a remarkable effect on bleaching fog.

In the color developing composition for color negative film, bromine ions are usually 0.2 × 10 ^{−2 to} 15.0 × 10 ⁻² mol / liter, preferably 0.5 × 10 ^{−2 to} 5.0 ×. In many cases, it is contained at 10 ⁻² mol / liter, but bromine ions are usually released into the processing composition as a by-product of development, and therefore often need not be added to the replenisher. Further, iodine ions are often contained in an amount of 0.2 × 10 ^{−3 to} 15.0 × 10 ⁻³ mol / liter, preferably 0.5 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / liter. In general, iodine ions are also sometimes released into the processing composition as a by-product of development, so that it is often unnecessary to add them to the replenisher.

In addition, color development processing compositions for color paper usually contain 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter of chlorine ions. Since it is released into the developer as a product, it is often unnecessary to add it to the replenisher.

  Next, the rinsing or stabilizing solution will be described.

  The rinse or stabilizing solution that can be used in the present invention includes chelating agents (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (potassium carbonate, borate, acetic acid). Salts, phosphates, etc.), antifungal agents (Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent brighteners (triazinyl stilbene series) Compounds), antioxidants (ascorbates, etc.), water-soluble metal salts (zinc salts, magnesium salts, etc.), and the like, which are usually contained in a stable solution, can be used as appropriate.

Furthermore, it is preferable that the rinsing or stabilizing solution contains sulfite, bisulfite or metabisulfite from the viewpoint of storage stability, and any organic or inorganic substance may be used as long as it releases sulfite ions. Are preferably inorganic salts. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L in the stabilizing solution, more preferably from 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L. To be added. Further, the pH of the rinsing or stabilizing solution is preferably in the range of 4.0 to 10.0. A pH adjusting agent for adjusting to the pH can also be contained. The pH adjuster may be any of commonly known alkali agents or acid agents.

  Next, the rinse or stabilization process of the present invention will be described.

  The time required for the rinsing or stabilization treatment step is a preferred embodiment under rapid processing conditions such as 90 seconds or less, or even 66 seconds or less. The time required for the rinsing or stabilization treatment step refers to the time from when the photosensitive material is immersed in the first vessel until it leaves the final vessel when the step has a plurality of vessels, and the next treatment from the final vessel. The process, for example, the drying process does not include the time for the photosensitive material to move. However, the crossover time between tanks in the case of having a plurality of tanks is included. The number of the rinsing tank or stabilization treatment tank may be one, but the number of tanks can be increased up to about 2 to 10 tanks, and the replenishment amount of the rinsing or stabilization treatment composition is decreased by increasing the number of tanks. However, considering the downsizing of the automatic processor, about 2 to 6 tanks are preferable. The replenisher may be replenished in several places, but it is replenished to the tank on the downstream side in the photosensitive material transport direction, and its overflow liquid (when connected between the tanks by a pipe located below the liquid level, The so-called counter current system (multi-stage counter-current system) is preferably used, in which the solution flows through the tube into the front tank of the tank, and a cascade flow system is also included. More preferably, the last tank is replenished with two or more stable tanks, and the overflow liquid is sequentially poured into the previous tank.

  The crossover time of the rinsing or stabilizing treatment step is preferably 5 seconds or less, more preferably 3 seconds or less. Further, as means for shortening the crossover time, it can be achieved by using a conveying system such as a submerged blade as described in FIGS. 2 to 5 of JP-A-5-66540.

It is preferable to use the process temperature of a rinse or the stabilization process process at 20-70 degreeC, More preferably, it is 25-60 degreeC. After the rinsing or stabilization treatment, no water washing treatment is required, but surface washing or the like by a small amount of water washing in an extremely short time can be optionally performed. Further, the replenishment amount of the rinsing or stabilizing solution is preferably 250 ml or less, more preferably 180 ml or less, per 1 m ^{2 of the} photosensitive material to be processed.

Next, in the processing method applied to the present invention, a preferable mode in the case where development processing is performed using an automatic processor will be described. In the processing tank of the automatic processor of the present invention, it is preferable that the area (opening area) in contact with air is as small as possible in terms of preventing the deterioration of the liquid. For example, the opening area (cm ² ) is set to a liquid tank ( When the value divided by cm ³ ) is defined as the aperture ratio, the aperture ratio is preferably 0.01 (cm ⁻¹ ) or less.

  In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means floating on the liquid surface in the treatment tank and the replenishment tank. Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon and the like are preferable.

  In the processing tank of the automatic processor used in the present invention, it is preferable to perform so-called evaporation correction in which water corresponding to the evaporation of the processing liquid is supplied. A specific method for replenishing such water is not particularly limited, but in particular, a monitor water tank different from the bleach-fixing tank described in JP-A-1-2549591 and 1-2254960 is installed, and the monitor Calculate the amount of water evaporation in the tank, calculate the amount of water evaporation in the bleach-fixing tank from this amount of water evaporation, replenish the water to the bleach-fixing tank in proportion to this amount of evaporation, liquid level sensor, and overflow Evaporation correction method using a sensor and water corresponding to the amount of evaporation is added in anticipation and described in Japan Institute of Technology, Publication No. 94-49925, page 1, right column, line 26 to page 3, left column, line 28. As described above, a preferred evaporation correction method is to add a water amount calculated by a coefficient determined in advance based on information on the operation time, stop time, and temperature control time of the automatic processor.

Further, as a method for drying the photosensitive material, it is preferable to use a ceramic warm air heater, and the supply air volume is preferably 4 m ^{2 to} 20 m ³ per minute. The thermostat for preventing the heating of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached leeward or upwind through the radiating fin or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed. The optimum temperature is 45 to 55 ° C. for color negative films and 55 to 65 ° C. for color paper. The drying time is preferably 5 seconds to 2 minutes, more preferably 5 seconds to 60 seconds.

  Next, the silver halide color light-sensitive material applied to the processing method using the processing composition having bleaching ability of the present invention will be described.

  The silver halide color photographic light-sensitive material applicable to the processing method using the processing composition having bleaching ability of the present invention includes a wide variety of photographic elements having a silver halide light-sensitive layer on a support, such as a color negative film. , Color reversal film, color paper, and color movie film.

  The silver halide color photographic light-sensitive material according to the present invention mainly comprises a yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, a magenta dye-forming coupler-containing green light-sensitive silver halide emulsion layer on a support. It has a photographic constituent layer comprising at least one each of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have. In addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer to be described later if desired.

  Hereinafter, a configuration example of color paper which is a silver halide color photographic light-sensitive material will be described.

  The composition of the silver halide emulsion used in the light-sensitive material according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide. In particular, silver chlorobromide or silver chloroiodide containing 95 mol% or more of silver chloride is preferable because the effect of the present invention is remarkable. Further, from the viewpoint of rapid processability and process stability, a silver halide emulsion containing 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

  In the light-sensitive material according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used from the viewpoint of reducing softening of the characteristic curve in a high concentration region in short exposure at high illuminance. be able to. In this case, the portion containing silver bromide at a high concentration may be an epitaxy junction with silver halide grains or a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. There may only be regions of different composition. Further, the composition may change continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably the surface of silver halide grains or the apex of crystal grains.

  In the light-sensitive material according to the present invention, it is preferable to use silver halide grains containing heavy metal ions from the viewpoint of reducing softening in high-illuminance and short-time scanning exposure. Examples of heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, cadmium, zinc, mercury, etc. Examples include Group 12 transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

  When the heavy metal ion forms a complex, the ligand or ion includes, for example, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl And ammonia. Of these, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

  In order for silver halide grains to contain the above heavy metal ions, each heavy metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add at the arbitrary time in a process. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

The amount of the heavy metal ion added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and especially 1 × 10 ⁻⁸ mol or more and 5 or less per mol of silver halide. × 10 ⁻⁵ mol or less is preferable.

  In the light-sensitive material according to the present invention, any silver halide grains can be used. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  In the light-sensitive material according to the present invention, the silver halide grains are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions in the same layer.

  The particle size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 μm, considering rapid processability, sensitivity, and other photographic performance. It is in the range of 2 to 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed as a diameter or a projected area.

  The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably fluctuations. Two or more monodispersed emulsions having a coefficient of 0.15 or less are added to the same layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains having a shape other than a cube or a sphere. .

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used. The silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any method of acidic method, neutral method and ammonia method. The silver halide grains may be grown at once, or may be grown after preparing seed grains. The method of preparing the seed particles and the method of growing the particles may be the same or different.

  In addition, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but is obtained by the simultaneous mixing method. Is preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and a reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus that forms grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration may be used. Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the light-sensitive material according to the present invention can be used in combination of a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion, for example, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and among them, a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The addition amount of the sulfur sensitizer is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but is generally 5 × 10 ^{−10 to} 5 × 10 10 per mole of silver halide. The range of ⁻⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, for example, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferable that More preferably, it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol. As chemical sensitization of the silver halide emulsion according to the present invention, reduction sensitization may be used.

The silver halide emulsion used in the light-sensitive material according to the present invention is publicly known for the purpose of preventing fogging that occurs during the preparation process of the light-sensitive material, reducing performance fluctuations during storage, and preventing fogging that occurs during development. Antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include compounds represented by the general formula (II) described in the lower column of page 7 of JP-A-2-14636. Specific compounds include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl). Examples include compounds such as -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. 10 ⁻² mol is more preferred. Further, when added to a constituent layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-251840, page 308, and special dyes can be used. The dyes described in the specification of Kaihei 6-3770 and the dyes described in JP-A-11-119379 are preferably used. The infrared absorbing dye is described in the lower left column on page 2 of JP-A-1-280750. The compounds represented by the general formulas (I), (II) and (III) have preferable spectral characteristics, and are preferable without affecting the photographic characteristics of the silver halide photographic emulsion and without causing contamination by residual colors.

  It is preferable to add a fluorescent brightening agent to the light-sensitive material according to the present invention from the viewpoint of improving the white background. Preferred examples of the compound include compounds represented by the general formula II described in JP-A-2-232652.

  The light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  Any known compound can be used as the spectral sensitizing dye for spectral sensitization of the silver halide emulsion used in the light-sensitive material according to the present invention. No. 251840, page 28, BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green, and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17. These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As the coupler used in the light-sensitive material according to the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. However, typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 Representative are cyan dye-forming couplers having a spectral absorption maximum wavelength at ˜750 nm.

  As a cyan coupler that can be preferably used in the light-sensitive material according to the present invention, a pyrrolotriazole-based coupler is preferably used, and a coupler represented by the general formula (I) or (II) in JP-A-5-313324 and a special coupler. The couplers represented by general formula (I) in Kaihei 6-347960 and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in European Patents EP0488248 and EP0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051 are disclosed. Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 171185, 8-31360, and 8-339060 are also preferable.

  Further, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (among others of the coupler (42) listed as a specific example). A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole cyan couplers described in EP 0456226A1, and pyrroloimidazole cyan couplers described in EP 0484909 are used. You can also.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.

  In the present invention, as the magenta coupler used in the magenta image forming layer, for example, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler is used. A pyrazolotriazole coupler in which a secondary or tertiary alkyl group as described in JP-A-61-65245 is directly linked to the 2, 3, or 6-position of a pyrazolotriazole ring, described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent No. 226,849A No. 6 and No. 294,785A as described in the 6th position. Use of pyrazoloazole couplers having an Kokishi group or an aryloxy group. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present application. As part of the specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  Further, examples of a yellow coupler that can be preferably used in the light-sensitive material according to the present invention include an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in an acyl group described in European Patent EP 0447969A1, and European Patent EP 0482552A1. Malondianilide type yellow coupler having a cyclic structure described in the specification, European Patent Nos. 935870A1, 953871A1, 953872A1, 953873A1, and 953874A1 Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide couplers described in US Pat. No. 5,118,599 and dioxane described in US Pat. No. 5,118,599 Reed with structure Acetamide type yellow couplers are preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.

  When using an oil-in-water emulsion dispersion method as a method of adding a coupler or other organic compound used in the light-sensitive material according to the present invention, it is usually necessary for a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. Accordingly, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. Examples of high-boiling organic solvents that can be used to dissolve and disperse couplers include phthalates such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phthalate. Are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group can also be used.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described in JP-A-2-66541, page 3, and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A No. 64-90445 and a metal complex represented by the general formulas XII, XIII, XIV, and XV described in JP-A No. 62-182741 are particularly preferable for magenta dyes. . Further, compounds represented by the general formula I 'described in JP-A-1-196049 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in JP-A-4-114154, page 9, lower left column, compound (A ' -1) etc. can be used. In addition, the fluorescent dye releasing compound described in US Pat. No. 4,774,187 can also be used.

  In the light-sensitive material according to the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, and is added to the silver halide emulsion layer to cause fogging. It is preferable to improve. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are the compounds represented by the general formula II described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 of the same, and compound 1 described on page 17 Is mentioned.

  In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds include compounds represented by general formula III-3 described in JP-A-1-250944 and general compounds described in JP-A-64-66646. Compounds represented by formula III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, described in JP-A-5-165144 And compounds represented by the general formulas (I) and (II).

  In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, simple substances. Hydrophilic colloids such as synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As the binder hardener, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination, for example, as described in JP-A Nos. 61-249054 and 61-245153. It is preferable to use the compound of. In order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the surface physical properties of the photosensitive material before or after processing, it is preferable to add a slipping agent or matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

  The photosensitive material according to the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but a plurality of color image forming layers as necessary. A unit may be formed by.

  In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-251840, page 308, and JP-A-6 A dye described in No. 3770 is preferably used.

  The light-sensitive material according to the present invention has at least one hydrophilic colloid layer colored with a non-diffusible compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable. As the coloring substance, a dye or other organic or inorganic coloring substance can be used.

The light-sensitive material according to the present invention preferably has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. The layer may contain a white pigment. For example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, and titanium dioxide is particularly preferable for various reasons. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / m 2} .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, an undercoat layer as required, or a non-photosensitive hydrophilic colloid layer such as an intermediate layer at an arbitrary position Can be provided.

  In the light-sensitive material according to the present invention, a whitening property can be further improved by adding a fluorescent brightening agent. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  In the light-sensitive material according to the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, and is added to the silver halide emulsion layer to cause fogging and the like. It is preferable to improve. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

  In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and compounds represented by general formula III described in JP-A 64-66646. Compounds represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, general formula I described in JP-A No. 4-1633, general formula (I) described in JP-A No. 5-165144, The compound shown by (II) is mentioned.

  The light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  When an oil-in-water emulsion type dispersion method is used to add the stain inhibitor or other organic compound used in the silver halide photosensitive material of the present invention, it is usually a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or higher. In addition, if necessary, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. As high-boiling organic solvents that can be used to dissolve and disperse stain inhibitors, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time until the coating after addition to the coating solution should be short, and 10 hours each. Is preferably within 3 hours, and more preferably within 20 minutes.

  As the support used for the photosensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white pigment. Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is used further sheet of 70~120g / m ² is preferred.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  The resin layer of the paper support having a water-resistant resin layer on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained.

  The photosensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic properties, dimensional stability) 1 or 2 or more subbing layers for improving the properties, friction resistance, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  Hereinafter, typical components of a color film which is a silver halide color photographic light-sensitive material will be described.

  For example, the details are described in the following Research Disclosure (hereinafter abbreviated as RD) and can be referred to.

  For example, RDNo. 17643, pp. 22-23 (December 1979), “1. Emulsion preparation and types”, and RD No. 18716, p. 648, “Photophysics and Chemistry” by Grakide, published by Paul Monter (P. Glkides, Chimie et Physiquegraph, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (GF). Daufin, Photographic Emulsion Chemistry Focal Press 1966), “Production and Coating of Photographic Emulsions” by Zerikman et al., Published by Focal Press (V.L. Can be prepared using methods. As the emulsion, monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,665,394 and British Patent 1,413,748 are also preferable.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RDNo. 17643, RDNo. 18716 and RDNo. 308119 (hereinafter abbreviated as RD17643, RD18716, and RD308119, respectively). The description part is shown below. In addition, each numerical value described below represents the described page.
[Item] [Page of RD308119] [RD17643] [RD18716]
Chemical sensitizer 996 III-A 23 648
Spectral sensitizer 996 IV-AA,
B, C, D, 23-24 648-649
H, I, J Item Supersensitizer 996 IV-AE, J Item
23-24 648-649
Antifoggant 998 VI 24-25 649
Stabilizer 998 VI 24-25 649
Known photographic additives that can be used in the silver halide color photographic light-sensitive material of the present invention are also described in the RD. The following is a relevant description.
[Item] [Page of RD308119] [RD17643] [RD18716]
Anti-turbidity agent 1002 VII-I Item 25 650
Dye Image Stabilizer 1001 VII-J Item 25
Brightener 998V 24
UV absorber 1003VIII-I,
Item XIII-C 25-26
Light absorber 1003VIII 25-26
Light scattering agent 1003VIII
Filter dye 1003VIII 25-26
Binder 1003IX 26 651
Antistatic agent 1006XIII 27 650
Hardener 1004X 26 651
Plasticizer 1006XII 27 650
Lubricant 1006XII 27 650
Activating agent / Coating aid 1005XI 26-27 650
Matting agent 1007XVI
Developer (contained in silver halide color photographic materials)
1001XXB Various couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in the above RD. The following is a relevant description.

[Item] [Page of RD308119] [RD17643]
Yellow Coupler 1001 VII-D Item VIIC-G Item Magenta Coupler 1001 VII-D Item VIIC-G Cyan Coupler 1001 VII-D Item VIIC-G Item Colored Coupler 1002 VII-G Item VIIG Item DIR Coupler 1001VII-F Item VIIF Item BAR Coupler 1002VII- Item F Release of other useful residues 1001VII-F Item Coupler Alkali-soluble coupler Item 1001VII-E The above additives can be added by the dispersion method described in RD308119XIV.

  In the silver halide color photographic light-sensitive material according to the present invention, auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned item RD308119VII-K can be provided.

  The silver halide color photographic light-sensitive material according to the present invention can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in the above-mentioned item RD308119VII-K.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<< Preparation of silver halide color photographic material >>
In accordance with the following method, a color paper which is a silver halide color photographic material for reflection viewing was prepared.

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, the reflective support A was prepared by laminating a melted polyethylene containing a dispersion of anatase-type titanium oxide (content: 15% by mass) on the side on which each emulsion layer was applied. After the reflective support A was subjected to corona discharge treatment, a gelatin subbing layer was provided, and each constituent layer having the following constitution was further applied to prepare a sample 101 which was a color paper. However, in Tables 1 and 2, the addition amount of the silver halide emulsion is described in terms of silver.

In the preparation of the sample 101, (H-1) and (H-2) were added as hardeners. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

  The details of each additive listed in Tables 1 and 2 are as follows.

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Disulfosulfonic acid di (2-ethylhexyl) sodium SU-3: Disulfosulfonic acid di (2,2,3,3,4,4,5 , 5, -octafluoropentyl) · sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro -6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ-3: 2,5-di-sec- Tetradecyl hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl Idroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone Image stabilizer A: pt-octylphenol Image stabilizer B: Poly (t-butylacrylamide)

(Preparation of silver halide emulsion)
<Preparation of blue-sensitive silver halide emulsion>
EMP-1, which is a monodispersed cubic emulsion having an average particle size of 0.71 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99.5 mol%, was prepared according to a conventional method. Next, EMP-1B, a monodispersed cubic emulsion having an average particle size of 0.64 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99.5 mol%, was prepared according to a conventional method.

  The following compounds were used for the above EMP-1, and chemical sensitization was performed so as to optimize the sensitivity-fogging relationship. Similarly, EMP-1B is chemically sensitized so that the sensitivity-fogging relationship is optimized, and then sensitized EMP-1 and EMP-1B are mixed in a silver ratio of 1: 1. A blue-sensitive silver halide emulsion (Em-B) was prepared.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ₋₄ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
<Preparation of green sensitive silver halide emulsion>
EMP-2, a monodispersed cubic emulsion having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method. Next, EMP-2B, a monodispersed cubic emulsion having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method.

  The following compounds were used for the EMP-2, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly, EMP-2B is chemically sensitized so that the sensitivity-fogging relationship is optimized, and then sensitized EMP-2 and EMP-2B are mixed in a silver ratio of 1: 1. A green sensitive silver halide emulsion (Em-G) was prepared.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 4 × 10 ⁻⁴ mol / mol AgX
<Preparation of red-sensitive silver halide emulsion>
EMP-3, a monodispersed cubic emulsion having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method. EMP-3B, a monodispersed cubic emulsion having an average particle size of 0.38 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5%, was prepared according to a conventional method.

  The following compounds were used for EMP-3, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly, EMP-3B is chemically sensitized so that the sensitivity-fogging relationship is optimized, and then sensitized EMP-3 and EMP-3B are mixed at a silver ratio of 1: 1. A red-sensitive silver halide emulsion (Em-R) was prepared.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Details of the respective compounds used for the preparation of the above silver halide emulsions are as follows.

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole and red photosensitivity To the silver halide emulsion, SS-1 was added at 2.0 × 10 ⁻³ mol per mol of silver halide.

<Development processing>
After the above-prepared sample 101 was subjected to wedge exposure according to a conventional method, the processing time of NPS-808GOLD manufactured by Konica Minolta Photo Imaging Co., Ltd. was used, and an automatic processor in which each processing tank was modified to satisfy the following conditions Then, development processing was performed under the following processing conditions and processing solutions (the bleach-fixing processing solutions are 1-1 to 1-14).

(Processing conditions)
Processing process Processing temperature Processing time Tank capacity
(℃) (sec) (L)
Color development 39.5 22 12.5
Bleach fixing 38.0 14 12.3
Stabilization-(1) 38.0 18 11.8
Stabilization-(2) 38.0 18 11.8
Stabilization-(3) 38.0 18 11.8
Dry 60-80 20
The crossover time between the treatment tanks was 2 seconds for all treatment steps.

(Processing liquid composition)
<Color developing composition tank solution: per liter>
Polyethylene glycol # 4000 15.0g
Sodium p-toluenesulfonate 10.0g
Potassium chloride 4.0g
4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl)
Aniline sulfate 7.0g
N, N-bis (sulfoethyl) hydroxylamine disodium salt 6.0 g
Potassium carbonate 33.0g
Diethylenetriaminepentaacetic acid 11.0g
pH 10.20
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Bleach fixer tank solution: per liter>
Aminopolycarboxylic acid ferric complex salt (described in Table 3) 0.15 mol
Additives (compounds listed in Table 3) listed in Table 3 ammonium thiosulfate (75% by weight aqueous solution) 0.55 mol
Ammonium sulfite (40 mass / volume% aqueous solution) 0.12 mol
Succinic acid 20.0g
pH 6.0
Water was added to 1 L, and the pH was adjusted with an aqueous ammonia solution or 50% sulfuric acid.

<Stabilizing liquid tank liquid: per 1L>
1-hydroxyethylidene-1,1-diphosphonic acid trisodium salt 3.0 g
Ethylenediaminetetraacetic acid 1.5g
o-Phenylphenol 0.1g
Sodium sulfite 0.5g
pH 7.5
Water was added to 1 L, and the pH was adjusted with an aqueous ammonia solution or 50% sulfuric acid.

  The details of the aminopolycarboxylic acid ferric complex salts and additives listed in Table 3 are as follows.

<Aminopolycarboxylic acid ferric complex salt>
EDTA-FeNH ₄ : Ferric ammonium ethylenediaminetetraacetate EDTA-FeNa: Sodium ferric ethylenediaminetetraacetate DTPA-FeNH ₄ : Ferric ammonium diethylenetriaminepentaacetic acid s, s-EDDS-FeNH ₄ : Ethylenediamine disuccinic acid second Iron ammonium In addition, s, s-EDDS-FeNH ₄ used the s, s form of an optical isomer.

<Additive>
Ti-1: Titanium oxide (TiO ₂ )
Ti-2: Barium titanate Ti-3: Ammonium hexafluorotitanate [(NH ₄ ) ₂ TiF ₆ ]
Ti-4: Potassium titanium oxalate dihydrate [K ₂ TiO (C ₂ O ₄ ) ₂ · 2H ₂ O]
<Evaluation of processing characteristics>
[Evaluation of recoloring properties]
After measuring the cyan reflection density D _R1 of the maximum density portion of the sample subjected to the above development processing with a red light using an X-rite densitometer, it was immersed in the following rebleaching solution at 35 ° C. for 3 minutes, and then washed with water. Then, the cyan density D _R2 of the maximum density part was measured again using an X-rite densitometer, and the cyan density difference ΔD _R at this time was obtained from the following formula, and this was used as a measure of the color recovery property. . As the absolute value of [Delta] D _R is smaller the better the recoloring property.

Cyan density difference ΔD _R = (cyan density D _R1 before _rebleaching ) − (cyan density D _R2 after _rebleaching )
<Rebleaching solution composition>
800ml water
Ethylenediaminetetraacetic acid ferric ammonium 0.075 mol
pH 7.0
Water was added to 1 L, and the pH was adjusted with ammonia or 50% sulfuric acid.

[Evaluation of desilvering properties]
The amount of residual silver (μg / cm ² ) in the maximum density portion of the development sample was measured using a fluorescent X-ray measuring device, and this was used as a measure of desilvering property. It shows that it is excellent in desilvering property, so that residual silver amount is small.

  The results obtained as described above are shown in Table 3.

  As is clear from the results shown in Table 3, by using the bleach-fixing processing composition of the present invention containing a titanium compound, good recoloring and desilvering properties can be obtained even in rapid processing compared to the comparative example. You can see that Moreover, it turns out that the especially excellent color-removing property and desilvering property are obtained by containing a titanium oxide compound among titanium compounds. In the bleach-fixing solution of the present invention to which a titanium compound was added, although a small amount of insoluble matter was observed, no adhesion or scratches were observed on the developed sample, and it was confirmed that there was no problem in practical use. .

Example 2
In the bleach-fixing solution 1-8 described in Example 1, the amount of titanium oxide added to iron ions was changed as described in Table 4, and the processing time of the bleach-fixing step was set to 12 seconds. The sample (L size: 127 mm × 89 mm) prepared in Example 1 was subjected to black solid exposure, processed 50 times continuously, and then processed in the same manner as described in Example 1. The wedge-exposed sample 101 was processed and the wedge-exposed sample was evaluated for color recovery and desilvering in the same manner as described in Example 1. Further, the surface of the photosensitive material that had been subjected to black solid exposure was visually observed, and stain adhesion resistance was evaluated according to the following criteria.

[Evaluation of dirt adhesion resistance]
◎: No dirt adheres to the front or back of the sample ○: Slightly adheres to the front or back of the sample △: Although there is no actual harm, adherent to the front or back of the sample is observed X: The quality obtained by the above is shown in Table 4 with the quality which becomes a problem in practical use, when clear dirt adhesion is recognized on the surface and back surface of a sample.

As is apparent from the results shown in Table 4, when the processing time of the bleach-fixing processing step is increased, the titanium oxide, which is a titanium compound, is 2 × with respect to iron ions of ethylenediaminetetraacetic acid ferric ammonium. It can be seen that by containing 10 ⁻⁵ mol% or more, good recoloring and desilvering properties are exhibited. Further, when titanium oxide is contained at 8 × 10 ⁻³ mol% or less with respect to iron ions, it is found that there is particularly little occurrence of recoloring failure and there is no contamination of the photosensitive material during processing. .

Example 3
<< Production of Single Part Bleach Fixing Concentrated Composition Packaging (Kit): Filling 1000ml >>
Bleaching and fixing concentrated composition shown below, with the addition of the ethylenediaminetetraacetic acid ferric complex salt or ethylenediaminetetraacetic acid ferrous complex salt and the additives listed in Table 5 so that the Fe (II) value ratio shown in Table 5 is obtained The air was blocked in a plastic bottle having an oxygen permeability of 5 ml / (m ² · day · atm) and kept tightly sealed to prepare single-part bleach-fixed concentrate kits 3-1 to 3-12.

[Bleach Fixing Concentrated Composition]
Ammonium sulfite (40 mass / volume%) 0.58 mol
Ammonium thiosulfate (75% mass / volume) 1.1 mol
Ethylenediaminetetraacetic acid ferric complex salt listed in Table 5 Ethylenediaminetetraacetic acid ferrous complex salt listed in Table 5 Additive (TiO ₂ ) listed in Table 5 Succinic acid 76.0 g
pH 4.8
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or 50% sulfuric acid.

  The above ethylenediaminetetraacetic acid ferrous complex salt is prepared by dissolving 1.02 mol mol of ethylenediaminetetraacetic acid with water and an aqueous ammonia solution with respect to ferrous sulfate heptahydrate and ferrous sulfate and stirring them. Prepared.

[Preparation of replenisher for bleach-fixing solution]
The bleach-fixing concentration kit prepared above was diluted 2.0 times with water to prepare a bleach-fixing solution replenisher.

[Running process]
Using the above-prepared bleach-fixing replenisher, the photosensitive material 101 produced in Example 1 was subjected to running processing (continuous processing) using the following processing conditions and processing solutions (the bleach-fixing replenisher uses 3-1 to 3-12). Treatment). At this time, the bleach-fixing solution tank solution used was prepared by adjusting the pH of the bleach-fixing solution replenisher to 6.0. The development processor used was a modified version of NPS-808 GOLD manufactured by Konica Minolta Photo Imaging Co., Ltd. so as to satisfy the following processing conditions.

  The running process was performed by 0.55R per day until it reached 2R. Here, 2R means that the bleach-fixing replenisher for the capacity of the bleach-fixing tank is replenished twice. In addition, both the bleach-fixing concentration kit of the present invention and the bleach-fixing replenisher to which the titanium compound was added, although a trace amount of insoluble matter was observed, did not cause clogging of the replenishment pump or filter of the developing processor in the running process. It was confirmed that there was no problem in practical use.

(Processing process)
Processing process Processing temperature Processing time Tank capacity Replenishment amount
(° C) (seconds) (L) (ml / m ² )
Color development 39.8 22 12.5 45
Bleach fixing 38.0 18 12.3 35
Stabilization-(1) 38.0 18 11.8
Stabilization-(2) 38.0 18 11.8
Stabilization-(3) 38.0 18 11.8 120
Dry 60-80 20
In addition, the stabilization process was set as the counter-current system of stabilization- (3)-> stabilization- (2)-> stabilization- (1).

(Processing liquid composition)
The color developer composition and stabilizing solution tank solution and replenisher solution are shown below.

<Color developing composition: per liter>
Tank liquid Replenisher Polyethylene glycol # 4000 15.0 g 15.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Potassium chloride 4.0 g −
4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl)
Aniline sulfate 6.0 g 12.0 g
N, N-bis (sulfoethyl) hydroxylamine disodium salt
4.0g 8.0g
Potassium carbonate 33.0g 33.0g
Diethylenetriaminepentaacetic acid 11.0 g 11.0 g
pH 10.20 12.40
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Stabilizing liquid: per 1L>
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid trisodium 3.0 g
Ethylenediaminetetraacetic acid 1.5g
o-Phenylphenol 0.1g
Sodium sulfite 0.5g
pH 7.5
Water was added to 1 L, and the pH was adjusted with an aqueous ammonia solution or 50% sulfuric acid.

<Evaluation of processing characteristics>
About each sample which performed the said development process, it carried out similarly to the method as described in Example 1, and evaluated recoloring property and desilvering property, and Table 5 shows the result obtained.

  As is apparent from the results shown in Table 5, even in the running process using the bleach-fixing replenisher prepared from the bleach-fixing concentrated composition comprising the one-part composition of the present invention, it was excellent in recoloring and desilvering properties. It turns out that an effect is demonstrated. Moreover, it turns out that the said effect is exhibited more on the conditions whose ratio of Fe (II) value is 50 mol% or more among the combinations of this invention.

Example 4
<< Preparation of silver halide color photographic material >>
In accordance with the following method, a color negative film which is a silver halide color photographic light-sensitive material for photographing was produced.

  The following composition was coated on a 125 μm thick cellulose triacetate film support provided with an undercoat layer to prepare Sample 201 which is a silver halide color photographic light-sensitive material for photographing consisting of multiple layers.

Hereinafter, in all the descriptions, the addition amount of each additive in the silver halide color photographic light-sensitive material is shown in grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver are shown in terms of metallic silver, and sensitizing dyes are shown in moles per mole of silver halide.

(First layer: antihalation layer)
Black colloidal silver 0.18
Ultraviolet absorber (UV-1) 0.3
Colored coupler (CM-1) 0.08
Colored coupler (CC-1) 0.05
High boiling point organic solvent (OIL-1) 0.16
High boiling point organic solvent (OIL-2) 0.5
Gelatin 1.5
(Second layer: Intermediate layer)
Colored coupler (CC-1) 0.035
High boiling point organic solvent (OIL-2) 0.08
Gelatin 0.7
(3rd layer: low sensitivity red photosensitive layer)
Silver iodobromide emulsion a 0.30
Silver iodobromide emulsion b 0.06
Sensitizing dye (SD-1) 1.10 × 10 ⁻⁵
Sensitizing dye (SD-2) 5.40 × 10 ⁻⁵
Sensitizing dye (SD-3) 1.25 × 10 ⁻⁴
Cyan coupler (C-1) 0.30
Colored coupler (CC-1) 0.054
DIR compound (DI-1) 0.02
High boiling point organic solvent (OIL-2) 0.3
Compound (AS-2) 0.001
Gelatin 1.5
(Fourth layer: Medium sensitivity red photosensitive layer)
Silver iodobromide emulsion b 0.37
SD-1 1.50 × 10 ⁻⁵
SD-2 7.00 × 10 ⁻⁵
SD-3 1.65 × 10 ⁻⁴
C-1 0.23
CC-1 0.038
DI-1 0.01
OIL-2 0.27
AS-2 0.001
Gelatin 1.5
(Fifth layer: High-sensitivity red photosensitive layer)
Silver iodobromide emulsion a 0.04
Silver iodobromide emulsion b 0.18
Silver iodobromide emulsion c 0.50
SD-1 1.30 × 10 ⁻⁵
SD-2 6.00 × 10 ⁻⁵
SD-3 1.40 × 10 ⁻⁴
C-1 0.12
C-2 0.03
CC-1 0.03
DI-1 0.004
OIL-2 0.19
AS-2 0.002
Gelatin 1.2
(6th layer: Intermediate layer)
OIL-1 0.08
AS-1 0.08
Gelatin 0.9
(Seventh layer: low-sensitivity green photosensitive layer)
Silver iodobromide emulsion a 0.22
Silver iodobromide emulsion d 0.09
SD-4 1.50 × 10 ⁻⁴
SD-5 3.75 × 10 ⁻⁵
M-1 0.35
CM-1 0.12
OIL-1 0.49
DI-2 0.017
AS-2 0.0015
Gelatin 2.2
(Eighth layer: Medium sensitivity green photosensitive layer)
Silver iodobromide emulsion d 0.46
SD-5 2.10 × 10 ⁻⁵
SD-6 1.61 × 10 ⁻⁴
SD-7 2.40 × 10 ⁻⁵
M-1 0.1
CM-1 0.05
OIL-1 0.15
AS-2 0.001
Gelatin 1.6
(9th layer: High sensitivity green photosensitive layer)
Silver iodobromide emulsion a 0.03
Silver iodobromide emulsion e 0.47
SD-5 1.90 × 10 ⁻⁵
SD-6 1.43 × 10 ⁻⁴
SD-7 2.10 × 10 ⁻⁵
M-1 0.033
M-2 0.023
CM-1 0.023
DI-1 0.009
DI-2 0.0009
OIL-1 0.08
AS-2 0.002
Gelatin 1.2
(10th layer: Yellow filter layer)
Yellow colloidal silver 0.08
OIL-1 0.06
AS-1 0.8
Gelatin 0.9
(11th layer: low sensitivity blue-sensitive layer)
Silver iodobromide emulsion a 0.18
Silver iodobromide emulsion f 0.14
Silver iodobromide emulsion g 0.08
SD-8 1.15 × 10 ⁻⁴
SD-9 5.60 × 10 ⁻⁵
SD-10 2.56 × 10 ⁻⁵
Y-1 1.0
OIL-1 0.4
AS-2 0.002
FS-1 0.08
Gelatin 3.0
(12th layer: High sensitivity blue-sensitive layer)
Silver iodobromide emulsion g 0.30
Silver iodobromide emulsion h 0.30
SD-8 7.12 × 10 ⁻⁵
SD-10 2.39 × 10 ⁻⁵
Y-1 0.1
OIL-1 0.04
AS-2 0.002
FS-1 0.01
Gelatin 1.10
(13th layer: 1st protective layer)
Silver iodobromide emulsion i 0.3
UV-1 0.11
UV-2 0.53
Gelatin 0.9
(14th layer: 2nd protective layer)
PM-1 0.15
PM-2 0.04
WAX-1 0.02
Gelatin 0.55
In addition to the above composition, compounds SU-1, SU-2, viscosity modifier V-1, hardeners H-1, H-2, stabilizers ST-1, ST-2, antifoggant AF- 1, AF-2, AF-3, dyes AI-1, AI-2, AI-3 and preservative D-1 were appropriately added to each layer.

  Table 6 below shows a list of silver halide emulsions used for the preparation of Sample 201. In addition, the average particle diameter was shown by the particle size converted into the cube.

The silver iodobromide emulsions b, e, g, and h contain 1 × 10 ⁻⁷ to 1 × 10 ⁻⁶ mol / 1 mol Ag of iridium.

  Each emulsion other than the above silver iodobromide emulsion i is added with the above-mentioned sensitizing dye, and then added with sodium thiosulfate, chloroauric acid, potassium thiocyanate, etc. so that the fog-sensitivity relationship is optimized. Sensitized.

<< Exposure and development process >>
The prepared sample 201 was subjected to wedge exposure according to a conventional method, and processed with the following processing conditions and processing liquid to evaluate desilvering properties and recoloring properties. As the automatic processor, an experimental machine in which the processing tank and processing time of the automatic processor CL-KP46QA manufactured by Konica Minolta Photo Imaging Co., Ltd. were modified so as to satisfy the conditions of the following processing steps was used.

(Processing conditions)
<Processing process><Processingtime><Processingtemperature><Tankcapacity>
Color development 1 minute 40 seconds 40.0 ° C 16.4L
Bleaching 20 seconds 36.0 ° C 3.9L
Fixing-1 20 seconds 36.0 ° C 3.9L
Fixing-2 20 seconds 36.0 ° C 3.9L
Stability-1 18 seconds 36.0 ° C 3.2L
Stable-2 18 seconds 36.0 ° C 3.2L
Dry 30 seconds 60.0 ℃
(Processing liquid composition)
<Color developing composition tank solution: per liter>
Sodium sulfite 5.0g
Potassium carbonate 43.0g
Diethylenetriaminepentaacetic acid 5sodium 4.0 g
N, N-bis (sulfoethyl) hydroxylamine-disodium salt 3.0 g
Carium bromide 1.5g
2-Methylbenzimidazole 0.1g
Polyvinylpyrrolidone: K-17 2.0g
Sodium p-toluenesulfonate 5.0g
Lithium hydroxide 2.0g
Potassium iodide 2.0mg
4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 9.5 g
pH 10.30
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Blank solution tank solution: per 1L>
1,3-propylenediaminetetraacetic acid ferric ammonium 0.30 mol
1,3-propylenediaminetetraacetic acid 0.03 mol
Additives (compounds listed in Table 7) Ammonium bromide listed in Table 7 60.0 g
Maleic acid 70.0g
Succinic acid 40.0g
pH 3.6
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or 50% sulfuric acid.

<Fixing solution tank solution: per 1L>
Ammonium thiosulfate 2.0 mol
Sodium sulfite 15.0g
pH 7.0
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Stabilizing liquid tank liquid: per 1L>
m-Hydroxybenzaldehyde 0.5g
Ethylenediaminetetraacetic acid disodium 0.6g
β-cyclodextrin 0.2g
Potassium carbonate 1.0g
Benzenesulfin sodium 0.5g
pH 7.0
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Evaluation of processing characteristics>
[Evaluation of recoloring properties]
Cyan transmission density D _T1 of the maximum density portion of the sample subjected to the developing process, after measuring the red light using a X-rite densitometer, was immersed for 3 minutes at 35 ° C. to re bleaching solution below, rinsing , dried and measured cyan transmission density D _T2 of the maximum density portion with X-rite densitometer again, the difference [Delta] D _R of the cyan density at this time determined from the following formula, which a measure of Fukuirosei did. As the absolute value of [Delta] D _R is smaller the better the recoloring property.

Cyan density difference ΔD _R = (cyan density D _T1 before _rebleaching ) − (cyan density D _T2 after _rebleaching )
<Rebleaching solution composition>
800ml water
Ethylenediaminetetraacetic acid ferric ammonium 0.25 mol
pH 6.0
Water was added to 1 L, and the pH was adjusted with ammonia or 50% sulfuric acid.

[Evaluation of desilvering properties]
The amount of residual silver (μg / cm ² ) in the maximum density portion of the development sample was measured using a fluorescent X-ray measuring device, and this was used as a measure of desilvering property. It shows that it is excellent in desilvering property, so that residual silver amount is small.

  Table 7 shows the results obtained as described above.

  As is apparent from the results shown in Table 7, by using the bleaching solution of the present invention containing a titanium compound, good recoloring and desilvering properties can be obtained even in the rapid processing of a color negative film, compared to the comparative example. You can see that Moreover, it turns out that the especially outstanding bleaching performance is obtained for the bleaching liquid containing a titanium oxide compound among titanium compounds. In the bleaching solution of the present invention to which a titanium compound was added, although a small amount of insoluble matter was observed, no adhesion or scratches were observed on the developed sample, and it was confirmed that there was no practical problem.

Claims (5)

A processing composition for silver halide color photographic light-sensitive materials having bleaching ability, comprising a titanium compound. 2. The processing composition for a silver halide color photographic light-sensitive material having bleaching ability according to claim 1, wherein the titanium compound is titanium oxide. An iron complex salt is contained, and the titanium compound is contained in an amount of 2 × 10 ⁻⁵ mol% or more and 8 × 10 ⁻³ mol% or less with respect to the number of mols of iron ions of the iron complex salt. A processing composition for a silver halide color photographic light-sensitive material having the bleaching ability according to 1 or 2. A bleach-fixing concentrated composition comprising an iron complex salt and a thiosulfate and comprising a one-part composition, wherein the ratio of Fe (II) value to the total iron ions of the iron complex salt is 50 mol% or more The processing composition for a silver halide color photographic material having bleaching ability according to any one of claims 1 to 3. A processing method for a silver halide color photographic light-sensitive material, comprising processing using the processing composition for a silver halide color photographic light-sensitive material having bleaching ability according to any one of claims 1 to 4.