Color developing agent, processing composition and color image-forming method

BACKGROUND OF THE INVENTION
The present invention relates to a new silver halide developing agent for color photography, a processing composition containing the developing agent, and a method for forming a color image with the processing composition. In particular, the present invention relates to a developing agent for color photography suitable for rapid processing of color photographs to form an image having only a slight fog and a high fastness, a processing composition containing the developing agent, and a method for forming a color image with the processing composition.
As mini-labs for processing photosensitive materials within the shops and the amount of color negative films used in the field of news photos are increasing recently, the demand for completion of the development process in a shorter time to immediately provide the prints to the customers or to immediately place the photo in newspapers or the like is rapidly increasing. The demand for reduction of the processing time is becoming more and more eager in processing color negative films, since the time necessitated therefor is longer than that necessitated for processing color papers.
The reduction in the processing time is possible by changing the color developing agent in the development of a color photographic photosensitive materials mainly comprising a silver bromoiodide emulsion such as color negative films. It was found that the processing time can be remarkably reduced with a 4-dialkylaminoaniline having an alkoxy group at 2-position as described in Japanese Patent Unexamined Published Application (hereinafter referred to as "J. P. KOKAI") Nos. Hei 5-113635 and Sho 53-69035 and U.S. Pat. No. 2,304,953. It was also found that the processing time can be reduced with 6-amino-1,2,3,4-tetrahydroquinolines or 5-amino-2,3-dihydroindoles as described in J. P. KOKAI No. Hei 4-45440.
However, it was found that the development of a photosensitive material for color photography which mainly comprises a silver bromoiodide emulsion with one of the compounds described in these specifications has some defects. Namely, since the image density in the unexposed part is high to cause a fog, the yellow and cyan image densities are insufficient as compared with the magenta image density in the exposed part, the three-colors are not well balanced. In addition, the fastness of the obtained image is also insufficient.
SUMMARY OF THE INVENTION
The present invention has been completed under these circumstances. The object of the invention is to provide a color developing agent suitable for use in the rapid processing method to form an image having only a slight fog, sufficient yellow and cyan image densities and a high image fastness, a processing composition containing the developing agent for the photosensitive silver halide material for color photography, and a method for forming a color image with the processing composition. This and other objects of the present invention will be apparent from the following description and Examples.
The above-described problem has been solved by use of a color developing agent represented by the following general formula (D): ##STR2## wherein R.sup.1 and R.sup.2 each represent an alkyl group, R.sup.3 represents a substituent, n represents an integer of 0 to 2 and Z represents a non-metallic atomic group forming a 5-membered or 6-membered aromatic ring and containing 1 to 3 carbon atoms,
According to another aspect of the present invention, there is provided a processing composition for color photography which comprises at least one of the color developing agent of the general formula (D).
There is also provided a method for forming a color image which comprises a step of developing an image-exposed silver halide photosensitive material for color photography in the presence of the color developing agents of the formula (D).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The alkoxy-type developing agents concretely described in J. P. KOKAI Nos. Hei 5-113635 and Sho 53-69035 and U.S. Pat. No. 2,304,953 have only a poor three-color balance and a high fog density, while they have rapid processing properties. The tetrahydroquinoline and dihydroindole developing agents described in J. P. KOKAI No. Hei 4-45440 are even worse. After intensive investigations on the developing agents represented by the above general formula (D), the inventors have found that they have rapid-processing properties equal to those of the alkoxy-type developing agents and, in addition, they are remarkably capable of overcoming the defect of the alkoxy-type developing agents.
The method for forming the color image with the color developing agent represented by the general formula (D) has advantages in that the rapid process is possible; fog density is low; the balance of the three colores, i.e. yellow, magenta and cyan, obtained by the rapid process is excellent; density and gradation changes in the running process are only slight; even when halogen ions (particularly chlorine and bromine ions) are accumulated, the influence thereof on the photographic properties is only slight; and the image thus formed has a high fastness.
Z in the general formula (D) for the compound of the present invention forms the aromatic ring. When Z does not form the aromatic ring, the color developing activity of the color developing agent is often not exhibited.
The detailed description will be made on R.sup.1, R.sup.2, R.sup.3, n and Z in the general formula (D) of the compounds of the present invention.
R.sup.1 and R.sup.2 each represent a substituted or unsubstituted, linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms. Examples of the alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, 1-methylpropyl, isobutyl, t-butyl, 1-ethylpropyl, 2-methylbutyl, isopentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Among them, methyl, ethyl, n-proyl, isopropyl, isobutyl, t-butyl, n-pentyl and n-hexyl groups are preferred. Methyl, ethyl, n-propyl, isopropyl and n-butyl groups are particularly preferred. Examples of the substituents include hydroxyl group, halogen atoms (such as fluorine and chlorine atoms), aryl groups (preferably those having 6 or 7 carbon atoms such as phenyl and m-hydroxyphenyl groups), heterocyclic groups (preferably five-membered or six-membered, saturated or unsaturated heterocyclic groups containing 1 to 5 carbon atoms and one or more oxygen, nitrogen or sulfur atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, imidazolyl and pyrazolyl groups), alkoxy groups (preferably those having 1 to 7 carbon atoms such as methoxy, ethoxy, 2-hydroxyethoxy and 2-methanesulfonylethoxy groups), aryloxy groups (preferably those having 6 or 7 carbon atoms such as phenoxy and p-hydroxyphenoxy groups), acylamino groups (preferably those having 1 to 7 carbon atoms such as acetamido, 2-methoxypropionamido and p-hydroxybenzoylamido groups), alkylamino groups (preferably those having 1 to 7 carbon atoms such as dimethylamino, diethylamino and 2-hydroxyethylamino groups), anilino groups (preferably those having 6 or 7 carbon atoms such as anilino, m-nitroanilino and m-hydroxyanilino groups), ureido groups (preferably those having 1 to 7 carbon atoms such as ureido, methylureido, N,N-diethylureido and 2-methanesulfonamidoethylureido groups), sulfamoylamino groups (preferably those having 0 to 7 carbon atoms such as dimethylsulfamoylamino, methylsulfamoylamino and 2-methoxyethylsulfamoylamino groups), alkylthio groups (preferably those having 1 to 7 carbon atoms such as methylthio, ethylthio and benzylthio groups), arylthio groups (preferably those having 6 or 7 carbon atoms such as phenylthio, 2-carboxyphenylthio and 4-hydroxyphenylthio groups), alkoxycarbonylamino groups (preferably those having 2 to 7 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino and 3-methanesulfonylpropoxycarbonylamino groups), sulfonylamino groups (preferably those having 1 to 7 carbon atoms such as methanesulfonamido, p-toluenesulfonamido and 2-methoxyethanesulfonamido groups), carbamoyl groups (preferably those having 1 to 7 carbon atoms such as carbamoyl, N,N-dimethylcarbamoyl and N-ethylcarbamoyl groups), sulfamoyl groups (preferably those having 0 to 7 carbon atoms such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl groups), sulfonyl groups (preferably aliphatic sulfonyl groups having 1 to 5 carbon atoms or aromatic sulfonyl groups having 6 or 7 carbon atoms such as methanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl groups), alkoxycarbonyl groups (preferably those having 1 to 7 carbon atoms such as methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl groups), heterocyclic oxy groups �five-membered or six-membered, saturated or unsaturated heterocyclic oxy groups containing 1 to 5 carbon atoms and one or more oxygen, nitrogen or sulfur atoms, wherein the number and kind of the hetero atom(s) constituting the ring may be one or more, such as 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy and 2-pyridyloxy groups!, azo groups (preferably those having 1 to 7 carbon atoms such as phenylazo, 2-hydroxyphenylazo and 4-sulfophenylazo groups), acyloxy groups (preferably those having 1 to 7 carbon atoms such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy groups), carbamoyloxy groups (preferably those having 1 to 7 carbon atoms such as N,N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy groups), silyl groups (preferably those having 3 to 7 carbon atoms such as trimethylsilyl, isopropyldiethylsilyl and t-butyldimethylsilyl groups), silyloxy groups (preferably those having 3 to 7 carbon atoms such as trimethylsilyloxy and triethylsilyloxy groups), aryloxycarbonylamino groups (preferably those having 7 carbon atoms such as phenoxycarbonylamino and 4-hydroxyphenoxycarbonylamino groups), imido groups (preferably those having 4 to 7 carbon atoms such as N-succinimido group), heterocyclic thio groups (five-membered or six-membered, saturated or unsaturated heterocyclic thio groups having 1 to 5 carbon atoms and at least one oxygen, nitrogen or sulfur atom, wherein the number and kind of the hetero atom(s) constituting the ring may be one or more, such as 2-benzothiazolylthio and 2-pyridylthio groups), sulfinyl groups (preferably those having 1 to 7 carbon atoms such as methanesulfinyl, benzenesulfinyl and ethanesulfinyl groups), phosphonyl groups (preferably those having 2 to 7 carbon atoms such as methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl groups), aryloxycarbonyl groups (preferably those having 7 carbon atoms such as phenoxycarbonyl and 3-hydroxyphenoxycarbonyl groups), and acyl groups (preferably those having 1 to 7 carbon atoms such as acetyl, benzoyl and 4-hydroxybenzoyl groups).
Examples of preferred substituents include hydroxyl, aryl, carboxy, sulfo, acylamino, ureido, sulfamoylamino, sulfonylamino, carbamoyl and sulfamoyl groups. Among them, hydroxyl, carboxy, sulfo, sulfonylamino, carbamoyl and sulfamoyl groups are particularly preferred.
Preferred examples of R.sup.1 and R.sup.2 include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-pentyl, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl, 3-uredopropyl and 2-sulfamoylaminoethyl groups. Among them, particularly preferred are methyl, ethyl, n-propyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-ureidoethyl, 2-carbamoylethyl, 2-sulfamoylethyl and 2-sulfamoylaminoethyl groups.
R.sup.3 represents a substituent. The substituent is a substituted or unsubstituted, linear, branched or cyclic alkyl group having 1 to 15, preferably 1 to 8 carbon atoms, and also is the same as the substituent described above with reference to R.sup.1 and R.sup.2.
Preferred examples of R.sup.3 includes methyl, ethyl, n-propyl, isopropyl, t-butyl, n-pentyl, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl, 3-uredopropyl, 4-hydroxycyclohexyl, 2,3,4-trihydroxybutyl, 2-sulfamoylaminoethyl, hydroxy, aryl, carboxy, sulfo, acylamino, ureido, sulfamoylamino, sulfonylamino, carbamoyl and sulfamoyl groups. Among them, particularly preferred are methyl, ethyl, n-propyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-ureidoethyl, 2-carbamoylethyl, 2-sulfamoylethyl, 2-sulfamoylaminoethyl, hydroxy, carboxy, sulfo, sulfonylamino, carbamoyl and sulfamoyl groups.
n represents an integer of 0 to 2. n is preferably 0 to 1, more preferably 0.
z is a non-metallic atomic group forming a five-membered or six-membered aromtic ring and containing 1 to 3 carbon atoms which may have a substituent. Atoms other than carbon atoms are nitrogen, oxygen and sulfur atoms. Among them, nitrogen and oxygen atoms are preferred. Examples of the aromatic rings include pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, furan, isoxazole, oxazole, thiophene, isothiazole and thiazole. Among them, pyrrole, furan and thiophene (which may have a substituent) are preferred. Further, pyrrole and furan (which may have a substituent) are particularly preferred. The substituents of the aromatic ring are the same as those described above with reference to R.sup.3.
In a preferred combination of R.sup.1, R.sup.2, R.sup.3 and Z, R.sup.1 and R.sup.3 each represent a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms which may be unsubstituted or substituted with a hydroxyl or sulfonylamino group, R.sup.3 represents a hydrogen atom and Z represents a pyrrole, furan or thiophene. In a more preferred combination, R.sup.1 and R.sup.2 each represent a linear or branched alkyl group having 1 to 4 carbon atoms which may be unsubstituted or substituted with a hydroxyl or sulfonylamino group, R.sup.3 represents a hydrogen atom and Z represents a pyrrole or furan. Concretely, preferred combinations are: (R.sup.1, R.sup.2, R.sup.3, Z)=�2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n=0), pyrrole)!, �ethyl, ethyl, hydrogen atom (n=0), pyrrole)!, �ethyl, 2-hydroxyethyl, hydrogen atom (n=0), pyrrole)!, �3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n=0), pyrrole)!, �4-hydroxybutyl, 4-hydroxybutyl, hydrogen atom (n=0), pyrrole)!, �2-methylsulfonylaminoethyl, 2-methylsulfonylaminoethyl, hydrogen atom (n=0), pyrrole)!, �2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n=0), furan!, �3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n=0), furan!, �4-hydroxybutyl, 4-hydroxybutyl, hydrogen atom (n=0), furan!, �ethyl, 2-carboxyethyl, hydrogen atom (n=0), furan!, �3,4-dihydroxybutyl, 3,4-dihydroxybutyl, hydrogen atom (n=0), furan!, �ethyl, 3-hydroxypropyl, hydrogen atom (n=0), furan!, �2-hydroxyethyl, 3-hydroxypropyl, hydrogen atom (n=0), furan!, �methyl, methyl, hydrogen atom (n=0), pyrrole! and �2,3,4-trihydroxybutyl, 2,3,4-trihydroxybutyl, hydrogen atom (n=0), pyrrole!. Among them, particularly preferred combinations are: (R.sup.1, R.sup.2, R.sup.3, Z)=�methyl, methyl, hydrogen atom (n=0), pyrrole!, �2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n=0), pyrrole)!, �3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n=0), pyrrole)!, �4-hydroxybutyl, 4-hydroxybutyl, hydrogen atom (n=0), pyrrole)!, �2-methylsulfonylaminoethyl, 2-methylsulfonylaminoethyl, hydrogen atom (n=0), pyrrole)!, �2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n=0), furan!, �3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n=0), furan! and �4-hydroxybutyl, 4-hydroxybutyl, hydrogen atom (n=0), furan!.
Examples of the typical developing agents represented by the general formula (D) in the present invention will be given below, which by no means limit the invention. ##STR3##
Since the compounds of the general formula (D) are very unstable when they are stored in the form of the free amines, it is usually preferred to keep them in the form of salts thereof with an inorganic or organic acid so that they can be converted into the free amines when they are added to the processing solution. The inorganic and organic acids for forming the salts of the compounds of the general formula (D) include, for example, hydrochloric, sulfuric, phosphoric, p-toluenesulfonic, methanesulfonic and naphthalene-1,5-disulfonic acids. Among them, sulfuric acid or p-toluenesulfonic acid is preferably used for forming the salts. Sulfuric acid is particularly preferably used.
(Synthesis Examples)
<Synthesis of compound (D-1)>
The compound (D-1) of the present invention was synthesized according to the following reaction scheme: ##STR4## �Synthesis of compound (2)!
21.1 g of reduced iron, 0.2 g of ammonium chloride, 0.2 ml of acetic acid and 20 ml of water were fed into a three-necked flask and then stirred for 30 minutes while the internal temperature was kept at 88.degree. C. by heating. 100 ml of isopropyl alcohol was added to the reaction mixture and the resultant mixture was stirred for additional 10 minutes under heating under reflux. 10.2 g of 4-nitroindole (the process for synthesizing this compound is described in Beilstein, Vol. 20, No. 3, p. 3194) was added to the obtained mixture slowly for the duration of 5 minutes. The mixture was stirred for additional 2 hours under heating under reflux. The reaction liquid was filtered through Celite. The filtrate was concentrated with a rotary evaporator to obtain the concentrate, which was used as it was in the subsequent step.
�Synthesis of compound (3)!
30 ml of tetrahydrofuran was added to the compound (2) obtained in the above-described step to obtain a solution. 20.6 g of bromoethane was dropped into the solution under stirring and heating under reflex. 10.6 g of sodium hydrogencarbonate was added thereto and the resultant mixture was directly stirred under heating and reflux for 2 hours. After leaving the reaction mixture to cool to room temperature followed by extraction with 100 ml of ethyl acetate and 50 ml of water, the obtained ethyl acetate layer was washed with a liquid mixture of 30 ml of saturated aqueous common salt solution and 50 ml of water three times, dried over anhydrous sodium sulfate and concentrated with a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 5.5 g of the intended compound (3) �yield: 46% based on the compound (1)!.
NMR (DMSO-d6): .delta.=10.93 (brs, 1H), 7.1 to 7.2 (m, 1H), 6.8 to 7.0 (m, 2H), 6.3 to 6.5 (m, 2H), 3.31 (q, 4H, J=6.9 Hz), 0.96 (t, J=6.9 Hz).
�Synthesis of compound (4)!
17.1 ml of hydrochloric acid was added to 6.48 g of 2,5-dichloroaniline. An aqueous solultion of 3.04 g of sodium nitrite in 6 ml of water was dropped into the resultant mixture under stirring and cooling with ice for 5 minutes. Then the stirring was continued for additional 10 minutes. Separately, 13.1 g of sodium acetate and 50 ml of methanol were added to 5.00 g of the compound (3). The reaction solution prepared from 2,5-dichloroaniline was added to the resultant mixture under stirring and cooling with ice for 5 minutes. Then the stirring was continued for additional 30 minutes and 200 ml of ethyl acetate and 100 ml of water were added to the reaction mixture to conduct the extraction. The ethyl acetate layer thus obtained was washed with a liquid mixture of 30 ml of saturated common salt solution and 70 ml of water three times, dried over anhydrous sodium sulfate and concentrated with a rotary evaporator. The obtained residue was dissolved in a mixed solution of 5 ml of tetrahydrofuran and 20 ml of ethyl acetate and the obtained solution was cooled with ice. The crystals thus precipitated were filtered under suction to obtain 4.9 g of the intended compound (4) (yield: 51%).
NMR (DMSO-d6): .delta.=11.62 (brs, 1H), 7.82 (d, 1H, J=2.0 Hz), 7.72 (d, 1H, J=8.7 Hz), 7.65 (d, 1H, J=8.7 Hz), 7.4 to 7.5 (m, 1H), 7.33 (dd, 1H, J=2.0, 8.7 Hz), 6.7 to 6.8 (m, 1H), 6.60 (d, 1H, J=8.7 Hz), 3.76 (q, 4H, J=6.7 Hz), 1.33 (t, 6H, J=6.7 Hz).
�Synthesis of compound (D-1)!
0.5 g of 10% palladium/carbon catalyst and 30 ml of ethanol were added to 4.9 g of the compound (4), and the obtained mixture was stirred in an autoclave at room temperature for 8 hours while hydrogen pressure was kept at 50 atm. The reaction mixture was filtered through Celite, and the filtrate was concentrated with a rotary evaporator. The residue was purified by silica gel column chromatography. A solution of 2.4 g of naphthalene-1,5-disulfonic acid in 10 ml of ethanol was added to the purified product, and crystals thus formed were filtered under suction to obtain 0.90 g of naphthalene-1,5-disulfonic acid salt of the intended compound (D-1) (yield: 14%).
NMR (DMSO-d6): .delta.=10.71 (brs, 1H), 8.91 (d, 2H, J=8.7 Hz), 8.00 (d, 2H, J=8.7 Hz), 7.5 to 7.7 (m, 1H), 7.47 (dd, 2H, J=8.7, 8.7 Hz), 7.25 (d, 1H, J=8.7 Hz), 6.8 to 7.0 (m, 2H), 6.80 (brs, 4H), 3.70 (q, 4H, J=6.7 Hz), 0.90 (t, 6H, J=6.7 Hz).
<Synthesis of compound (D-10)>
The compound (D-10) of the present invention was synthesized according to the following reaction scheme: ##STR5## �Synthesis of compound (7)!
207 g of potassium carbonate, 10 g of sodium iodide and 450 ml of N,N-dimethylformamide were added to 139.1 g of the compound (5). 128 g of the compound (6) was dropped into the obtained mixture under stirring for 10 minutes while the internal temperature was kept at 85.degree. C. and the resultant mixture was directly stirred under heating and reflux for 3 hours. After leaving the reaction mixture to cool to room temperature followed by extraction with 1000 ml of ethyl acetate and 1200 ml of water, the obtained ethyl acetate layer was washed with a mixed solution of 300 ml of saturated aqueous common salt solution and 500 ml of water five times, dried over anhydrous sodium sulfate and concentrated with a rotary evaporator. 194.6 g of the intended compound was obtained by distillation of the residue (yield: 93%).
NMR (CDCl.sub.3): .delta.=7.85 (dd, 1H, J=3.0, 9.0 Hz), 7.66 (d, 1H, J=3.0 Hz), 7.46 (dd, 1H, J=9.0, 9.0 Hz), 7.20 (dd, 1H, J=3.0, 9.0 Hz), 4.75 (q, 1H, J=7.0 Hz), 2.23 (s, 3H), 1.56 (d, 3H, J=7.0 Hz).
�Synthesis of compound (8)!
130.5 g of the compound (7) was dissolved in 400 ml of methylene chloride. 175 ml of sulfuric acid was dropped into the solution under stirring for 30 minutes while it was heated under reflux. The stirring under heating and reflux was continued for additional 4 hours and then the reaction mixture was left to cool to room temperature and poured into 1 kg of ice. 1000 ml of ethyl acetate and 200 g of common salt were added to the resultant mixture to conduct the extraction. The ethyl acetate layer thus formed was washed with a mixed solution of 300 ml of saturated aqueous common salt solution and 300 ml of water three times. After drying over anhydrous sodium sulfate followed by concentration with a rotary evaporator, 200 ml of methanol was added to the concentrate to form crystals, which were then filtered by suction to obtain 53 g of the intended compound (8) (yield: 44%).
NMR (CDCl.sub.3): .delta.=7.90 (d, 1H, J=9.0 Hz), 7.60 (d, 1H, J=9.0 Hz), 7.23 (dd, 1H, J=9.0, 9.0 Hz), 2.45 (s, 3H), 2.27 (s, 3H).
�Synthesis of compound (9)!
20 ml of water was added to a mixture of 36.5 g of reduced iron, 1 g of ammonium chloride and 1 ml of acetic acid, and the resultant mixture was stirred for 10 minutes while the internal temperature was kept at 85.degree. C. by heating. 100 ml of isopropyl alcohol was added to the mixture and the whole was stirred under heating and reflux for additional 10 minutes. 24.0 g of the compound (8) was added thereto and the resultant mixture was stirred for additional 3 hours while it was heated under reflux. After filtration through Celite, the filtrate was concentrated to obtain the compound (9) as the crude product, which was then used as it was in the subsequent step.
�Synthesis of compound (10)!
68.0 g of potassium carbonate and 100 ml of N,N-dimethylformamide were added to the compound (9) obtained as described above, and the resultant mixture was stirred under heating at an internal temperature of 60.degree. C. 52.6 g of ethyl bromoacetate was dropped into the obtained mixture for 10 minutes and the resultant mixture was directly stirred under heating at 60.degree. C. for 2 hours. After leaving the reaction mixture to cool to room temperature followed by extraction with 500 ml of ethyl acetate and 500 ml of water, the obtained ethyl acetate layer was washed with a mixed solution of 100 ml of saturated aqueous common salt solution and 300 ml of water four times, dried over anhydrous sodium sulfate and concentrated with a rotary evaporator. The intended compound (10) was obtained as the crude product, which was then used as it was in the subsequent step.
�Synthesis of compound (11)!
8.0 g of lithium aluminum hydride was suspended in 50 ml of tetrahydrofuran. A solution of the compound (10) obtained as described above in 50 ml of tetrahydrofuran was dropped into the suspension for 10 minutes. The obtained mixture was stirred at room temperature for 5 hours and then stirred under heating and reflux for 1 hour. 30 ml of ethyl acetate was dropped into the reaction mixture for 10 minutes. After stirring for additional 1 hour followed by dropping of 5 ml of saturated aqueous sodium sulfate solution, the resultant mixture was stirred for 10 minutes. After filtration through Celite, the filtrate was concentrated with a rotary evaporator to obtain the intended compound (11) as the crude product, which was then used as it was in the subsequent step.
�Synthesis of compound (12)!
62 ml of hydrochloric acid and 400 ml of methanol were added to 23.6 g of 2,5-dichloroaniline to obtain a solution. A solution of 11.1 g of sodium nitrite in 22 ml of water was dropped into the solution under stirring and cooling with ice for 10 minutes. Separately, 45 g of sodium acetate and 100 ml of methanol were added to the compound (11) obtained in the preceding step and the resultant mixture was stirred under cooling with ice. The reaction liquid obtained from 2,5-dichloroaniline as described above was added thereto. After stirring for additional 30 minutes followed by the extraction with 1000 ml of ethyl acetate and 800 ml of water, the ethyl acetate layer thus obtained was washed with 200 ml of saturated aqueous common salt solution and 400 ml of water four times. The product was dried over anhydrous sodium sulfate and then concentrated with a rotary evaporator. The residue thus obtained was purified by silica gel column chromatography to obtain 19.6 g of the intended compound (12) �yield: 37% based on the compound (8)!.
NMR (DMSO-d6): .delta.=7.6 to 7.7 (m, 3H), 7.45 (d, 1H, J=10.3, 3.0 Hz), 6.56 (d, 1H, J=10.0 Hz), 3.6 to 3.7 (m, 4H), 3.3 to 3.5 (m, 4H), 2.51 (s, 3H), 2.40 (s, 3H).
�Synthesis of compound (D-10)!
20 ml of ethanol was added to 4.90 g of the compound (12). 0.5 g of 10% palladium/carbon catalyst was added to the resultant mixture and then 5 ml of formic acid was dropped thereto for 5 minutes. The obtained mixture was directly stirred for 30 minutes and filtered through Celite. A solution of 2.1 g of naphthalene-1,5-disulfonic acid in ethanol was added to the filtrate. The crystals thus formed were filtered by suction to obtain 3.00 g of naphthalene-1,5-disulfonic acid salt of the intended compound (D-10) (yield: 47%).
NMR (DMSO-d6): .delta.=8.86 (d, 2H, J=9.0 Hz), 7.95 (d, 2H, J=9.0 Hz), 7.41 (dd, 2H, J=9.0 Hz), 6.97 (d, 1H, J=9.0 Hz), 6.63 (d, 1H, J=9.0 Hz), 3.67 (t, 4H, J=5.0 Hz), 3.27 (t, 4H, J=5.0 Hz), 2.36 (s, 3H), 2.33 (s, 3H).
<Synthesis of compound (D-41)>
The compound (D-41) of the present invention was synthesized according to the following reaction scheme: ##STR6## �Synthesis of compound (13)!
46.8 g (0.30M) of iodoethane was dropped into a mixed solution of 43.3 g (0.30M) of .delta.-aminoquinoline, 41.5 g of potassium carbonate and 200 ml of N,N-dimethylacetamide under stirring to conduct the reaction at 65.degree. C. for 2 hours. After leaving the reaction mixture to cool followed by addition of 500 ml of water thereto and extraction with 500 ml of ethyl acetate, the extract was washed with water (200 ml.times.three times). The extract was concentrated and then the product was separated and purified by silica gel column chromatography (developer: mixed solution of ethyl acetate and hexane) to obtain 34.7 g (67%) of the intended compound (13).
�Synthesis of compound (14)!
39.8 g (0.42M) of 3-chloropropyl alcohol was dropped into a mixed solution of 34.7 g (0.20M) of the compound (13), 41.5 g (0.30M) of potassium carbonate, 18 g (0.12M) of sodium iodide and 100 ml of N,N-dimethylacetamide under stirring at 120.degree. C. to conduct the reaction for additional 10 hours. 41.5 g of K.sub.2 CO.sub.3 and 19.9 g of 3-chloropropyl alcohol were added to the reaction mixture and the reaction was conducted at 120.degree. C. for 1 hour. The product was after-treated in the same manner as that of 13 and then purified by silica gel column chromatography to obtain 29.8 g (65%) of the intended compound (14).
�Synthesis of compound (15)!
8.9 g (0.055M) of 2,5-dichloroaniline was dissolved in a mixed solution of 20 ml of 12N hydrochloric acid and 10 ml of tetrahydrofuran. 15 ml of an aqueous solution of 3.8 g (0.055M) of sodium nitrite was dropped into the resultant solution under stirring and cooling with ice for 10 minutes. After conducting the reaction at 0.degree. C. for additional 1.5 hours, the reaction liquid was dropped into a solution of 11.5 g (0.050M) of the compound (14) and 24.6 g (0.30M) of sodium acetate in 80 ml of methanol under stirring and cooling with ice. After conducting the reaction at 0.degree. C. for 1 hour and then at room temperature for 2 hours, 150 ml of water was added to the reaction liquid. The product was extracted with 200 ml of ethyl acetate, washed with water, concentrated and purified by silica gel column chromatography to obtain 16.1 g (72.5%) of the intended compound (15).
�Synthesis of compound (D-41)!
8.1 g (0.020M) of the compound (15) and 1.0 g of 10% palladium/carbon were dispersed in 150 ml of ethanol and the reaction was conducted in hydrogen atmosphere at 40.degree. C. under 30 atm. The reaction mixture was filtered through Celite. 3.6 g of 1,5-naphthalenedisulfonic acid tetrahydrate was added to the filtrate, and the crystals thus formed were taken by filtration to obtain 7.5 g (70%) of 1,5-naphthalenedisulfonic salt of the intended compound (D-41).
NMR spectrum (D.sub.2 O): .delta.=0.92 (t, 3H), 1.75 (m, 2H), 3.5 (t, 2H), 3.7 (m, 4H), 7.4 (d, 1H), 7.7 (t+m, 2H+1H), 7.9 (d, 1H), 8.15 (d, 2H), 8.45 (m, 1H), 8.8 (d, 2H), 8.95 (m, 1H).
The color developing agent of the present invention can be used either singly or in combination with other known p-phenylenediamine derivatives. Typical examples of the compounds which can be used in combination with the color developing agent include the following compounds, which by no means limit them: N,N-diethyl-p-phenylenediamine (P-1), 4-amino-3-methyl-N,N-diethylaniline (P-2), 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline (P-3), 4-amino-N-ethyl-N-(2-hydroxyethyl)aniline (P-4), 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline (P-5), 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline (P-6), N-(2-amino-5-N,N-diethylaminophenylethyl)methane sulfonamide (P-7), N,N-dimethyl-p-phenylenediamine (P-8), 4-amino-3-methyl-N-ethyl-N-(2-methoxyethyl) aniline (P-9), 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline (P-10), and 4-amino-3-methyl-N-ethyl-N-(2-butoxyethyl)aniline (P-11). Among the above-described p-phenylenediamine derivatives to be used for the combination, particularly preferred are compounds P-3, P-5, P-6 and P-10. The p-phenylenediamine derivatives are usually used in the form of their salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates and naphthalene-1,5-disulfonates.
The processing composition may be in liquid form or solid form (such as powder, granules or tablets).
These compounds can be used in combination of two or more of them depending on the purpose. The aromatic primary amine developing agent is used in an amount of preferably about 0.001 to 0.2 mol, more preferably 0.005 to 0.1 mol, per liter of the color developer.
The color developer may contain a compound for directly preserving the above-described aromatic primary amine color developing agent, which is selected from among hydroxylamines described in J. P. KOKAI Nos. Sho 63-5341, Sho 63-106655 and Hei 4-144446, hydroxamic acids described in J. P. KOKAI No. Sho 63-43138, hydrazines and hydrazides described in J. P. KOKAI No. Sho 63-146041, phenols described in J. P. KOKAI Nos. Sho 63-44657 and Sho 63-58443, .alpha.-hydroxyketones and .alpha.-aminoketones described in J. P. KOKAI No. Sho 63-44656, and saccharides described in J. P. KOKAI No. Sho 63-36244. Such a compound can be used in combination with monoamines described in J. P. KOKAI Nos. Sho 63-4235, 63-24254, 63-21647, 63-146040, 63-27841 and 63-25654, diamines described in J. P. KOKAI Nos. Sho 63-30845, 63-14640 and 63-43139, polyamines described in J. P. KOKAI Nos. Sho 63-21647, 63-26655 and 63-44655, nitroxy radicals described in J. P. KOKAI No. Sho 63-53551, alcohols described in J. P. KOKAI Nos. Sho 63-43140 and 63-53549, oximes described in J. P. KOKAI No. Sho 63-56654 and tertiary amines described in J. P. KOKAI No. Sho 63-239447. The color developer may contain, if necessary, also a preservative selected from among metals described in J. P. KOKAI Nos. Sho 57-44148 and 57-53749, salicylic acids described in J. P. KOKAI No. Sho 59-180588, alkanolamines described in J. P. KOKAI No. Sho 54-3582, polyethyleneimines described in J. P. KOKAI No. Sho 56-94349 and aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 and the like. Particularly when the hydroxylamines are used, they are preferably used in combination with the above-described alkanolamines or aromatic polyhydroxy compounds.
Particularly preferred preservatives are hydroxylamines represented by general formula (I) given in J. P. KOKAI No. Hei 3-144446. Among them, compounds having methyl, ethyl, sulfo or carboxyl group are preferred. The preservative is used in an amount of 20 to 200 mmol, preferably 30 to 150 mmol, per liter of the color developer.
The color developer for the photosensitive material for prints contains preferably 3.0.times.10.sup.-2 to 1.5.times.10.sup.-1 mol/l, particularly preferably 3.5.times.10.sup.-2 to 1.0.times.10.sup.-1 mol/l, of chlorine ion. When the chlorine ion concentration is higher than 1.5.times.10.sup.-1 mol/l or particularly higher than 1.0.times.10.sup.-1 mol/l, the development is retarded, which is against the object of the present invention, i.e. to rapidly attain the high maximum density and, on the contrary, a chlorine ion concentration of below 3.0.times.10.sup.-2 mol/l is unsuitable for prevention of the fogging.
The color developer used in the present invention contains preferably 0.5.times.10.sup.-5 to 1.0.times.10.sup.-3 mol/l, more preferably 3.0.times.10.sup.-5 to 5.times.10.sup.-4 mol/l of bromine ion. When the bromine ion concentration is higher than 1.times.10.sup.-3 mol/l, the development is retarded, and the maximum density and sensitivity are lowered and, on the contrary, when it is below 0.5.times.10.sup.-5 mol/l, the fogging cannot be sufficiently prevented.
The chlorine ion and bromine ion can be directly added to the color developer or they can be dissolved out of the photosensitive material into the color developer in the course of the development.
When the chlorine ion is directly added to the color developer, the chlorine ion-feeding substances include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. The chlorine ion can be fed from a fluorescent brightener added to the color developer. The bromine ion-feeding substances include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide.
When the chlorine ion or bromine ion is dissolved out of the photosensitive material in the course of the development, such an ion can be fed by an emulsion or another substance.
The color developer of the present invention may further contain additives mentioned in the above-described J. P. KOKAI No. Hei 3-144446. For example, a compound selected from among carbonates, phosphates, borates and hydroxybenzoates mentioned on page 9 of the specification thereof can be used as a buffering agent for maintaining pH. pH of the color developer is kept preferably in the range of 9.0 to 12.5, more preferably in the range of 9.5 to 11.5, with such a buffering agent.
Antifoggants usable herein are halide ions and organic antifoggants mentioned on page 10 of that specification. Particularly when the concentration of the color developing agent in the color developer is as high as 20 mmol/l or above or when the processing temperature is as high as 40.degree. C. or above, a considerably high bromide e ion concentration is preferred. Namely, it is preferably 17 to 60 mmol/l . If necessary, the concentration can be controlled in a preferred range by removing the halogen with an ion exchange resin or ion exchange membrane.
The chelating agents preferably used herein are aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphoshonic acids and phosphonocarboxylic acids. They are typified by ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid) and salts of them. Preferred chelating agents are biodegradable compounds such as those mentioned in J. P. KOKAI Nos. Sho 63-146998, 63-199295, 63-267750 and 63-267751 and Hei 2-229146 and 3-186841, German Patent No. 3739610 and European Patent No. 468325.
The color developer of the present invention may contain, if necessary, also a development restrainer such as a benzimidazole, benzothiazole or mercapto compound; a development accelerator such as a benzyl alcohol, polyethylene glycol, quaternary ammonium salt or amine; a dye-forming coupler; a competitive coupler; an assistant developing agent such as 1-phenyl-3-pyrazolidone; a tackifier; and a surfactant such as an alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid or aromatic carboxylic acid.
If necessary, a development accelerator can be added to the color developer.
The development accelerators include thioether compounds described in Japanese Patent Publication for Opposition Purpose (hereinafter referred to as "J. P. KOKOKU") Nos. Sho 37-16088, 37-5987, 38-7826, 44-12380 and 45-9019 and U.S. Pat. No. 3,813,247; p-phenylenediamine compounds described n J. P. KOKAI Nos. Sho 52-49829 and 50-15554; quaternary ammonium salts described in J. P. KOKAI No. Sho 50-137726, J. P. KOKOKU No. Sho 44-30074 and J. P. KOKAI Nos. Sho 56-156826 and 52-43429; amine compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253,919, J. P. KOKOKU No. Sho 41-11431 and U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346; polyalkylene oxides described in J. P. KOKOKU Nos. Sho 37-16088 and 42- 25201, U.S. Pat. No. 3,128,183, J. P. KOKOKU Nos. Sho 41-11431 and 42-23883 and U.S. Pat. No. 3,532,501; as well as 1-phenyl-3- pyrazolidones and imidazoles. These development accelerators are usable, if necessary.
When the color developer is used for processing a photosensitive material for photography, the replenisher is fed in an amount of preferably 550 ml or below, more preferably 450 ml or below, most preferably 80 to 400 ml, per m.sup.2. By reducing bromide ion concentration in the replenisher or by using no bromide ion, the amount thereof can be reduced to 300 ml or below. In processing a photosensitive material for prints, the color developer replenisher is fed in an amount of 20 to 600 ml, preferably 30 to 200 ml and more preferably 40 to 100 ml, per m.sup.2 of the material.
In processing the photosensitive material for photography, the processing temperature with the color developer is preferably 35.degree. C. or above, more preferably 40.degree. to 50.degree. C. In processing the photosensitive material for prints, the processing temperature with the color developer is 20.degree. to 50.degree. C., preferably 30.degree. to 45.degree. C., and most preferably 37.degree. to 42.degree. C.
In processing the photosensitive material for photography, the processing time with the color developer is preferably 30 seconds to 3 minutes and 15 seconds, more preferably 30 seconds to 2 minutes and 30 seconds. In processing the photosensitive material for printing, the processing time with the color developer is usually shorter than 3 minutes, preferably 10 seconds to 1 minute and more preferably 10 to 30 seconds. The term "processing time" (such as development time) herein indicates the time necessitated from entering of the photosensitive material into a processing bath to entering of it into the next processing bath.
It is preferred that the developer for the photosensitive material for printing is substantially free from benzyl alcohol.
To control the change of the photographic chracteristics during the continuous process and also to attain the effect of the present invention, it is also preferred that the developer for the photosensitive material for printing is substantially free from sulfurous acid ion (the term "substantially free" herein indicates that sulfurous acid ion concentration is not higher than 3.0.times.10.sup.-3 mol/l). Sulfurous acid ion concentration is preferably not higher than 1.0.times.10.sup.-3 mol/l, and most preferably, the developer is free from sulfurous acid ion. It is to be noted, however, a very small amount of sulfurous acid ion used, before the preparation of the developer, for inhibiting the oxidation of the processing agent kit containing a concentrated developing agent is not included therein. To control the change of the photographic chracteristics depending on the change in concentration of a hydroxylamine, it is more preferred that the developer is substantially free from the hydroxylamine (the term "substantially free" herein indicates that the hydroxylamine concentration is not higher than 5.0.times.10.sup.-3 mol/l). It is most preferred that the developer is completely free from the hydroxylamine.
It is preferred to inhibit the evaporation of the developer and oxidation thereof by air. The contact area of the processing liquid with air in the processing vessel can be represented by the opening rate defined as follows:
Opening rate=�(contact area of processing solution with air(cm.sup.2)!/�volume of processing solution (cm.sup.3)!
The opening rate (cm.sup.-1) defined as above is preferably not higher than 0.05, more preferably in the range of 0.0005 to 0.01. The opening rate is reduced by covering the surface of the photographic processing solution in the processing vessel with a floating lid or the like, by providing a movable lid as described in J. P. KOKAI No. Hei 1-82033 or by a slit development process described in J. P. KOKAI No. Sho 63-216050. It is preferred that the processing solution in a color developer-replenishing tank or in a processing tank is sealded with a high-boiling organic solvent or a high-molecular compound to reduce the contact area thereof with air. It is particulrly preferred to use liquid paraffin, an organosiloxane or the like. The opening rate can be reduced not only in the color development and black-and-white development steps but also in all of the subsequent steps such as bleaching, bleach-fixing, fixing, water washing and stabilization steps.
The developer can be reused by regeneration. The term "regeneration of the developer" herein indicates that the used developer is treated with an anion exchange resin or by electrodialysis and that the activity of the developer is increased by adding a processing agent called "regenerating agent". The regeneration rate (rate of the overflow in the replenisher) is preferably at least 70%, particularly at least 90%.
The regeneration is conducted preferably with the anion exchange resin. Particularly preferred composition of the anion exchange resin and method for regeneration of the resin are those described in "Diaion Manual (I)" (Edition 14, 1986) published by Mitsubishi Chemical Industries Ltd. Among the anion exchange resins, preferred are those of a composition described in J. P. KOKAI Nos. Hei 2-952 and 1-281152.
The color-developed photosensitive material is then usually desilvered. The desilverization process herein basically comprises bleaching process and fixing process. Both processes can be conducted at the same time by a bleach-fixing process or these processes are combined with each other.
The bleaching agents include, for example, iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids; quinones; and nitro compounds. Typical bleaching agents are, for example, ferric chloride, ferricyanides, bichromates; organic complex salts of iron (III) (such as metal complex salts of aminopolycarboxylic acids, e.g. ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid); persulfates; bromates; permanganates; and nitrobenzenes. Among them, preferred are ferric aminopolycarboxylates and salts of them as described on page 11 of the above-mentioned J. P. KOKAI No. Hei 3-144446. Examples of them include ferric salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid. Other bleaching agents include complex salts of citric acid, tartaric acid and malic acid. Among them, particularly preferred are iron (III) complex salt of ethylenediaminetetraacetic acid and iron (III) complex salts of aminopolycarboxylic acids such as iron (III) complex salt of 1,3-diaminopropanetetraacetic acid. Such an iron (III) complex salt of aminopolycarboxylic acid is particularly effective in both bleaching solution and bleach-fixing solution.
The bleaching solution, bleach-fixing solution, pre-bleaching bath and pre-bleach-fixing bath may contain a bleaching accelerator, if necessary. Examples of the bleaching accelerators include compounds having a mercapto group or disulfido bond described in U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, J. P. KOKAI No. Sho 53-95630 and Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in J. P. KOKAI No. Sho 50-140129; thiourea derivatives described in U.S. Pat. No. 3,706,561; iodides described in J. P. KOKAI No. Sho 58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in J. P. KOKOKU No. Sho 45-8836; and bromide ions. Among them, compounds having a mercapto group or disulfido group and also having a remarkable accelerating effect are preferred. Particularly preferred are compounds described in U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812 and J. P. KOKAI No. Sho 53-95630. Further, compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach-accelerators may be added also to the photosensitive material. When a color photosensitive material for photography is to be bleach-fixed, these bleaching accelerators are particularly effective.
The desilvering bath may contain rehalogenating agents, pH buffering agents and other known additives as described on page 12 of J. P. KOKAI No. Hei 3-144446, in addition to the bleaching agent.
An organic acid is preferably incorporated into the bleaching solution and bleach-fixing solution in order to prevent a bleach stain, in addition to the above-described compounds. Particularly preferred organic acids are those having an acid dissotiation constant (pKa) of 2 to 6 such as acetic acid, propionic acid, hydroxyacetic acid, succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid and adipic acid. Particularly preferred are succinic, maleic and glutaric acids.
The pH of the bleaching solution and bleach-fixing solution is usually 4.0 to 8.0. For conducting the process more rapidly, pH can be further lowered.
The fixing agents usable for the fixing solution or bleach-fixing solution include, for example, thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodides. Among them, the thiosulfates are commonly used and ammonium thiosulfate is most widely usable. A combination of a thiosulfate with a thiocyanate, thioether compound or thiourea is also preferred.
Examples of preferred preservatives for the fixing solution and bleach-fixing solution include sulfites, hydrogensulfites, carbonylhydrogensulfite adducts and sulfinic acid compounds described in European Patent No. 294769 A. Further, it is preferred to add a chelating agent such as an aminopolycarboxylic acid or organic phosphonic acid to the fixing solution or bleach-fixing solution in order to stabilize it. Examples of preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N,N,N,N'-tetrakis(methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid and 1,2-propylenediaminetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred.
It is preferred to incorporate a compound having a pKa of 6.0 to 9.0 into the fixing solution or bleach-fixing solution in order to adjust pH thereof. For example, it is preferable that imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole should be incorporated thereto in an amount of 0.1 to 10 mol/liter.
The imidazole compounds herein indicate imidazole and derivatives thereof. Preferred substituents of imidazole include, for example, alkyl, alkenyl, alkynyl, amino and nitro groups and halogen atoms. The alkyl, alkenyl and alkynyl groups may be further substituted with an amino or nitro group or a halogen atom. The total carbon number of the substituents of imidazole is preferably 1 to 6. The most preferred substituent is methyl group.
Examples of the imidazole compounds will be given below, which by no means limit them: imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 4-(2-hydroxyethyl)-imidazole, 2-ethylimidazole, 2-vinylimidazole, 4-propylimidazole, 4-(2-aminoethyl) imidazole, 2,4-dimethylimidazole, and 2-chloroimidazole. Among them, preferred are imidazole, 2-methylimidazole and 4-methylimidazole. The most preferred is imidazole.
The fixing solution and bleach-fixing solution may further contain a fluorescent brightening agent; defoaming agent; surfactant; polyvinylpyrrolidone; methanol; etc.
When a replenishing system is employed, the quantity of the fixing solution or bleach-fixing solution to be used as the replenisher is preferably 100 to 3,000 ml, more preferably 300 to 1800 ml, per m.sup.2 of the photosensitive material. The bleach-fixing solution as the replenisher can be fed as a bleach-fixing replenisher or, as described in J. P. KOKAI No. Sho 61-143755 or Japanese Patent Application No. Hei 2-216389, overflowing bleaching solution and fixing solution can be used.
The total processing time in the desilvering step comprising bleaching, bleach-fixing and fixing of the photosensitive material for photography is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30.degree. to 60.degree. C., preferably 35.degree. to 55.degree. C.
In processing with a processing solution having a bleaching effect, it is particularly preferred to conduct aeration so as to keep the photographic properties very stable. The aeration can be conducted by a method known in the art, such as blowing of air into the solution having the bleaching effect or absorption of air with an ejector.
In the blowing of air, it is preferred to release air into the solution by means of a diffusing tube having fine pores. Such a type of diffusing tube is widely used for an aeration tank in the treatment of an activated sludge. In the aeration, techniques described on pages BL-1 to BL-2 of Z-121, Using Process C-41 (the third edition) published by Eastman Kodak Co. in 1982 can be employed. In the process of the present invention with the processing solution having bleaching effect, vigorous stirring is preferred. For the stirring, contents of J. P. KOKAI No. Hei 3-33847 (from line 6, right upper column to line 2, left lower column on page 8) can be employed as they are.
Silver can be recovered from the processing solution having the fixing effect by a well-known method, and the regenerated solution is usable. Silver can be recovered by an electrolysis method (French Patent No. 2,299,667), precipitation method (J. P. KOKAI No. Sho 52-73037 and German Patent No. 2,331,220), ion exchange method (J. P. KOKAI No. Sho 51-17114 and German Patent No. 2,548,237) and metal replacement method (British Patent No. 1,353,805). In these methods, silver is preferably recovered in line from the tank solution so as to improve the rapidness.
The processing solution having the bleaching effect is reusable by recovering the overflow used in the process and adding the components to regulate the composition thereof. Such a regeneration is easy in the present invention. The details of the regeneration are described on pages 39 to 40 of Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 Process (revised in August, 1990) published by Fuji Photo Film Co., Ltd.
Although the kit for preparing the processing solution of the present invention having the bleaching effect may be in the form of either liquid or powder, the powder is more easily prepared than the liquid, since most starting materials are in powder form having only a slight hygroscopicity after removal of ammonium salts.
Further, the kit for the regeneration is preferably in the form of a powder from the viewpoint of reduction in the quantity of waste water, since it can be directly added without using excess water.
For the regeneration of the processing solution having the bleaching function, a method described in "Shashin Kogaku no Kiso, -Gin'en Shashin Hen- (The Fundamentals of Photographic Engineering, -Edition of Silver Salt Photographs-)" (edited by Nihon Shashin Gakkai and published by Corona in 1979) can be employed in addition to the above-described aeration method. In particular, the bleaching solution can be regenerated by an electrolytic regeneration method or a method wherein hydrobromic acid, chlorous acid, bromine, a bromine precursor, a persulfate, and hydrogen peroxide, or a combination of a catalyst with hydrogen peroxide, bromous acid or ozone is used.
In the electrolytic regeneration method, a cathode and an anode are placed in the same bleaching bath, or the anodic bath is separated from the cathodic bath with a diaphragm. In another electrolytic regeneration method, the bleaching solution and developer and/or fixing solution can be regenerated at the same time by using a diaphragm.
The fixing solution and bleach-fixing solution are regenerated by electrolytically reducing silver ion accumulated therein. To maintain the fixing function, it is also preferred to remove the accumulated halogen ion with an anion exchange resin.
In the desilverizing steps, the stirring is conducted preferably as vigorously as possible by, for example, a method which comprises bumping a jet of the processing solution against the emulsion surface of the photosensitive material as described in J. P. KOKAI No. Sho 62-183460; a method wherein the stirring effect is improved with a rotating means as described in J. P. KOKAI No. Sho 62-183461; a method wherein the photosensitive material is moved while the emulsion surface thereof is brought into contact with a wiper blade provided in the solution so as to make the flow on the emulsion surface turbulent and thereby improving the effect of the stirring; and a method wherein the quantity of the circulating flow of the whole processing solutions is increased. Such a means of making the stirring vigorous is effective for any of the bleaching solution, bleach-fixing solution and fixing solution. Supposedly, the improvement in the stirring effect accelerates the feeding of the bleaching agent and fixing agent into the emulsion membrane, thereby increasing the desflverizing speed. The above-described means of improving the stirring effect are more effective when a bleaching accelerator is used. In such a case, the acceleration effect is further improved and inhibition of the fixing by the bleaching accelerator can be controlled.
An automatic developing machine used for developing the photosensitive material of the present invention preferably has a means of transporting the photosensitive material as described in J. P. KOKAI Nos. Sho 60-191257, 60-191258 and 60-191259. As described in J. P. KOKAI No. Sho 60-191257, such a transportation means remarkably reduces the amount of the processing solution brought from the preceding bath into the subsequent bath, so that the deterioration in the function of the processing solution can be remarkably prevented. Such a function is particularly effective in reducing the processing time in each step and also in reducing the amount of the replenisher.
After the desilverization process, the photosensitive material is usually washed with water. The step of washing with water may be replaced with a stabilization step. In the stabilization process, any of known methods described in J. P. KOKAI Nos. Sho 57-8543, 58-14834 and 60-220345 can be employed. Further, step of washing with water/stabilization step wherein a stabilization bath containing both dye stabilizer and a surfactant is used as the final bath can be employed.
Water used for washing and the stabilizing solution can contain a softening agent for hard water, such as an inorganic phosphoric acid, polyaminocarboxylic acid or organic aminophosphonic acid.
The amount of water used in the washing step or the like varies in a wide range depending on the properties of the photosensitive material (which depend on, for example, couplers used), use thereof, temperature of water, number of the tanks (number of stages), replenishing method such as counter flow or down-flow system and various other conditions. Two to four stages are preferred. The amount of the replenisher is 1 to 50 times, preferably 1 to 30 times and more preferably 1 to 10 times larger than that brought from the preceding bath per a unit area. A preferred method for efficiently reducing the amount of the replenisher is so-called multi-tank washing method or stabilizing method wherein the water washing tank or stabilizing tank is divided with a diaphragm so that the photosensitive material is processed in the liquid by passing it through a slit of a wiper blade or the like without being exposed to air.
Although the amount of water necessitated for washing can be remarkably reduced by the multi-stage counter flow method or multi-tank washing method, another problem is caused in this method that bacteria propagate themselves while water is kept for a longer time in the tanks and, as a result, a suspended matter thus formed is attached to the photosensitive material. For solving this problem, a very effective method for previously reducing the amount of calcium ion and magnesium ion described in J. P. KOKAI No. Sho 62-288,838 can be employed. Further, this problem can be solved also by using water previously sterilized with a germicide such as chlorinated sodium isocyanurates. Further, the water used for washing can contain isothiazolone compounds and thiabendazoles described in J. P. KOKAI No. Sho 57-8,542, known chlorine-containing germicides and benzotriazoles described in Hiroshi Horiguchi "Bokin Bobai-zai no Kagaku (Chemistry for Prevention of Bacteria and Fungi)" published by Sankyo Book Publishing Co. in 1986, "Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu (Technique of Sterilization and Prevention of Microorganisms)" edited by Eisei Gijutsu-kai and published by Kogyo Gijutsu-kai in 1982 and "Bokinbobai-zai Jiten (Dictionary of Steriliers and Antifungal Agents)" edited by Nippon Bokinbobai Gakkai and published in 1986.
The pH of washing water and the stabilizing solution is 4 to 9, preferably 5 to 8. The temperature and time which vary depending on the properties and use of the photosensitive material are usually 15.degree. to 45.degree. C. and 10 seconds to 10 minutes, preferably 25.degree. to 40.degree. C. and 15 seconds to 5 minutes, respectively. The photosensitive material can be processed directly with a stabilizing solution in place of washing with water. The stabilization can be conducted by any of known processes described in J. P. KOKAI Nos. Sho 57-8543, 58-14834 and 60-220345.
The stabilizing solution contains a compound which stabilizes the color image, selected from among, for example, formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde/bisulfite adduct, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, dimethylolurea, N-methylol compounds such as N-methylolpyrazole, organic acids and pH buffering agents. The preferred amount of these compounds is 0.001 to 0.02 mol per liter of the stabilizing solution. The free formaldehyde concentration in the stabilizing solution is preferably as low as possible so as to prevent formaldehyde gas from sublimation. From such a point of view as above, preferred color image stabilizers are m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolazoles described in J. P. KOKAI No. Hei 4-270344 such as N-methylolpyrazole and azolylmethylamines described in J. P. KOKAI No. Hei 4-313753 such as N,N'-bis(1,2,4-triazol-1-ylmethyl)piperazine. Particularly preferred is a combination of an azole such as 1,2,4-triazole with an azolylmethylamine such as 1,4-bis(1,2,4-triazol-1-ylmethyl)piperazine or a derivative thereof as described in J. P. KOKAI No. Hei 4-359249 (corresponding to European Patent Unexamined Published Application No. 519190 A 2), since a high image stability and a low formaldehyde vapor pressure are realized by the combination. The stabilizing solution preferably contains, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound of Bi, Al or the like, a fluorescent whitening agent, a hardener, an alkanolamine described in U.S. Pat. No. 4,786,583, and a preservative which can be contained in also the above-described fixing solution and bleach-fixing solution such as a sulfinic acid compound described in J. P. KOKAI No. Hei 1-231051.
Various surfactants can be incorporated into washing water and stabilizing solution so as to prevent the formation of water spots in the course of drying of the photosensitive material. Among them, preferred is an anionic surfactant, particularly an alkylphenol/ethylene oxide adduct. The alkylphenols are particularly preferably octyl-, nonyl-, dodecyl- and dinonylphenols. The molar number of ethylene oxide to be added is particularly preferably 8 to 14. It is also preferred to use a silicon Surfactant having a high antifoaming effect.
The washing water and stabilizing solution preferably contain a chelating agent. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N'-trimethylenephosphonic acid and diethylenetriamine-N,N,N',N'-tetramethylenephosphonic acid; and hydrolyzates of maleic anhydride polymers described in European Patent No. 345,172 A 1.
The overflow obtained during the washing with water and/or replenishing of the stabilizing solution is reusable in other steps such as the desilverizing step.
When each of the above-described processing solutions is concentrated by evaporation in the process with an automatic developing machine, it is preferred to replenish a suitable amount of water, correcting solution or process replenisher in order to compensate the solution for concentration caused by the evaporation. Although the method for replenishing water is not particularly limited, preferred are the following methods: a method described in J. P. KOKAI Nos. Hei 1-54959 and 1-254960 wherein a monitor water tank which is different from the bleaching tank is provided, the amount of water evaporated from the monitor water tank is determined, the amount of water evaporated from the bleaching tank is calculated from the determined amount of evaporated water, and water is fed into the bleaching tank in proportion to the amount of evaporated water; and a method described in J. P. KOKAI Nos. Hei 3-248155, 3-249644, 3-249645 and 3-249646 wherein the compensation for the evaporation is conducted with a liquid level sensor or overflow sensor. Although water for compensating for the evaporation in each processing solution may be tap water, deionized water or sterilized water preferably used in the above-described water washing steps is preferred.
Water processed with a reverse osmosis membrane is effectively usable for washing and/or stabilization. The materials usable for preparing the reverse osmosis membrane are, for example, cellulose acetate, crosslinked polyamides, polyethers, polysulfones, polyacrylic acids and polyvinylene carbonates.
From the viewpoints of the effect of prevention from staining and prevention from reduction in amount of passing water, the water-feeding pressure in the reverse osmosis with the membrane is preferably 2 to 10 kg/cm.sup.2, particularly preferably 3 to 7 kg/cm.sup.2.
The process with the reverse osmosis membrane is preferably conducted for water to be used in the second tank and/or a tank arranged thereafter for the washing in the multi-stage counter-current system and/or stabilization. In particular, when two tanks are used, the treated water is used in the second tank; when three tanks are used, the treated water is used in the second or third tank; and when four tanks are used, water in the third or fourth tank is treated with the reverse osmosis membrane and water passed through the membrane is returned into that tank (the tank from which the water to be treated with the reverse osmosis membrane was taken; hereinafter referred to as "tank from which water was taken") or into subsequent tank for washing with water and/or stabilization tank. In an embodiment, concentrated washing water and/or stabilizing solution is returned into a bleach-fixing bath on upstream side.
Each processing solution is used preferably at 10.degree. to 50.degree. C. Although the standard temperature ranges from 33.degree. to 38.degree. C., it is also possible to accelerate the process and thereby to reduce the process time at a higher temperature or, on the contrary, to conduct the process at a lower temperature so as to improve the image quality and stability of the processing solution.
Each processing solution is usable for processing two or more kinds of photosensitive materials. For example, a color negative film and a color paper are processed with the same solution to reduce the cost of the processing machine and to simplify the process.
The solutions are suitably used for various color photosensitive materials such as general color negative films, color negative films for movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. They are suitable also for film units having a lens described in J. P. KOKOKU No. Hei 2-32615 and Japanese Utility Model Publication for Opposition Purpose No. Hei 3-39784.
At least one photosensitive layer is formed on a support to form the photosensitive material. A typical example of the silver halide photosensitive material comprises at least one photosensitive layer (comprising two or more silver halide emulsion layers having substantially the same color sensitivity but different degree of sensitivity) formed on the support. The photosensitive layer is a unit photosensitive layer sensitive to any of blue, green and red lights. In the multi-layered silver halide photosensitive materials for color photography, the arrangement of the unit photosensitive layers is usually as follows: a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in this order from the support. However, the order may be reversed or a sensitive layer may be interposed between two layers sensitive to another color depending on the purpose. A photoinsensitive layer can be provided between the silver halide photosensitive layers or as the top layer or the bottom layer. These layers may contain a coupler, DIR compound or color-mixing inhibitor which will be described below. The two or more silver halide emulsion layers constituting the unit photosensitive layer have preferably a structure consisting of two layers, i.e. a high sensitivity emulsion layer and a low sensitivity emulsion layer, as described in DE 1,121,470 or GB 923,045. The arrangement of the layers is preferably such that the sensitivity thereof decreases gradually toward the support. An emulsion layer having a low sensitivity may be formed away from the support and an emulsion layer having a high sensitivity may be formed close to the support as described in J. P. KOKAI Nos. Sho 57-112751, 62-200350, 62-206541 and 62-206543.
Examples of the arrangement are as follows: a blue-sensitive layer having a low sensitivity (BL)/blue-sensitive layer having a high sensitivity (BH)/green-sensitive layer having a high sensitivity (GH) green sensitivive layer having a low sensitivity (GL)/red-sensitive layer having a high sensitivity (RH)/red-sensitive layer having a low sensitivity (RL); BH/BL/GL/GH/RH/RL; and BH/BL/GH/GL/RL/RH toward the support.
As described in J. P. KOKOKU No. Sho 55-34932, the arrangement may be a blue-sensitive layer/GH/RH/GL/RL toward the support. Another arrangement is a blue-sensitive layer/GL/RL/GH/RH toward the support as described in J. P. KOKAI Nos. Sho 56-252738 and 62-63936.
Another arrangement is that of three layers having sensitivities gradually lowered toward the support, i.e. a top layer (a silver halide emulsion layer having the highest sensitivity), middle layer (a silver halide emulsion layer having a lower sensitivity) and bottom layer (a silver halide emulsion layer having a sensitivity lower than that of the middle layer) as described in J. P. KOKOKU No. Sho 49-15495. Even in such an arrangement comprising three layers having sensitivities different from each other, layers sensitive to the same color may further comprise an emulsion layer having medium sensitivity/emulsion layer having high sensitivity/emulsion layer having low sensitivity in the order toward the support as described in J. P. KOKAI No. Sho 59-202464. In another example, the arrangement may be as follows: high-sensitivity emulsion layer/low sensitivity emulsion layer/medium sensitivity emulsion layer, or low sensitivity emulsion layer/medium sensitivity emulsion layer/high sensitivity emulsion layer. When the photosensitive material has four or more layers, the arrangement of them may be varied as described above.
For improving the color reproducibility, it is preferred to form a donor layer (CL) having an interlayer effect and a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL and RL at a position adjacent to or close to the main photosensitive layers as described in U.S. Pat. Nos. 4,663,271, 4,705,744 and 4,707,436 and J. P. KOKAI Nos. Sho 62-160448 and 63-89850.
When the photosensitive material is for prints (color photographic paper), the silver halide grains in the emulsions are spectrally sensitized with the blue-sensitive, green-sensitive and red-sensitive, spectrally sensitizing dyes in the above-described order of layers. This photosensitive material can be prepared by forming these layers in the above-described order on the support. The order of the layers can be changed. Namely, from the viewpoint of rapid process, it is preferred in some cases that the top photosensitive layer contains silver halide grains having the largest average grain size; and from the viewpoint of storability under irradiation with light, it is preferred that the bottom layer comprises a magenta photosensitive layer.
The photosensitive layer and the developed hue may be such which are unsuitable for the above-described function. One or more infrared-sensitive silver halide emulsion layers may also be formed.
Preferred silver halide used for preparing the photosensitive material for photography is silver bromoiodide, silver chloroiodide or silver chlorobromoiodide containing less than about 30 molar % of silver iodide. Particularly preferred is silver bromoiodide or silver chlorobromoiodide containing about 2 to 10 molar % of silver iodide.
The silver halide grains in the photographic emulsion may be in a regular crystal form such as a cubic, octahedral or tetradecahedral form; an irregular crystal form such as spherical or plate form; or a complex crystal form thereof. They include also those having a crystal fault such as a twin plate.
The silver halide grain diameter may range from about 0.2 .mu.m or less to as large as that having a projection area diameter of about 10 .mu.m. The emulsion may be either a polydisperse emulsion or monodisperse emulsion. Preferred is the monodisperse emulsion having a coefficient of dispersion of 15% or below, and more preferred is that having a coefficient of dispersion of 10% or below.
The silver halide photographic emulsion usable in the present invention can be prepared by processes described in, for example, Research Disclosure (hereinafter referred to as "RD") No. 17643 (December, 1978), pp. 22 to 23, "1. Emulsion preparation and types"; RD No. 18716 (November, 1979), p. 648; and RD No. 307105 (November, 1989), pp. 863 to 865.
Tabular grains having an aspect ratio of 3 or higher are also usable in the present invention. The tabular grains can be easily prepared by processes described in, for example, Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248 to 257 (1970); U.S. Pat. No. 4,434,226; and British Patent No. 2,112,157.
The crystal structure of the grains may be uniform; the grains may comprise an inside portion and an outside portion which are composed of silver halides different from each other; or the structure may be a laminated one. Different silver halide grains can be bonded together by an epitaxial bond or they can be bonded with a compound other than silver halides such as silver rhodanate or lead oxide. A mixture of grains having various crystal forms can also be used.
The emulsion may be of a surface-latent image type for forming a latent image mainly on the surface thereof, of an internal latent image type for forming a latent image in the grains or of such a type that a latent image is formed both on the surface and in the grains. The emulsion must be a negative one. In the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in J. P. KOKAI No. Sho 63-264740 may also be used. Processes for producing such an emulsion are described in J. P. KOKAI No. Sho 59-133542. The thickness of the shells in the emulsion which varies depending on the developing process is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.
The silver halide emulsion to be used in the present invention is usually physically and chemically ripened and spectrally sensitized. The additives to be used in these steps are shown in RD Nos. 17643, 18716 and 307105. The portions in which the additives are mentioned in these three Research Disclosures are summarized in a table given below.
A mixture of two or more photosensitive silver halide emulsions different from one another in at least one of grain size, grain size distribution, halogen components, shape of the grains and sensitivity can be used for forming a layer of the photosensitive material of the present invention.
Silver halide grains having the fogged surface described in U.S. Pat. No. 4,082,553, silver halide grains having fogged core and colloidal silver described in U.S. Pat. No. 4,626,498 and J. P. KOKAI No. Sho 59-214852 can be preferably used for forming the photosensitive silver halide emulsion layer and/or substantially photo-insensitive, hydrophilic colloid layer. The term "silver halide grains having fogged core or surface" indicates silver halide grains which can be subjected to uniform (non-imagewise) development irrespective of exposed or non-exposed parts of the photosensitive material. The silver halide for forming the core of the core/shell type silver halide grains having the fogged core may have the same or different halogen composition. The silver halide grains having the fogged core or surface include silver chloride, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide grains. The average grain size of the fogged silver halide grains is preferably 0.01 to 0.75 .mu.m, particularly 0.05 to 0.6 .mu.m. The grains may be in a regular form or in the form of a polydisperse emulsion. The dispersion is, however, preferably of monodisperse system.
Fine grains of a photo-insensitive silver halide are also usable. The term "fine grains of photo-insensitive silver halide" indicates fine silver halide grains which are not sensitized in the image-forming exposure for forming a dye image and which are substantially not developed in the developing process. They are preferably previously not fogged. The fine silver halide grains have a silver bromide content of 0 to 100 molar %. If necessary, they may contain silver chloride and/or silver iodide. They preferably contain 0.5 to 10 molar % of silver iodide. The fine silver halide grains have an average grain diameter (average diameter of a circle having an area equal to that of the projected area) of preferably 0.01 to 0.5 .mu.m, more preferably 0.02 to 0.2 .mu.m.
It is unnecessary to chemically sensitize or spectrally sensitize the silver halide fine grains. It is preferred, however, to incorporate a known stabilizer such as a triazole, azaindene, benzothiazolium or mercapto compound or a zinc compound thereinto prior to the incorporation thereof into a coating solution. Colloidal silver can be incorporated into the fine silver halide grain-containing layer.
The amount of silver to be applied to the photosensitive material for photography is preferably not more than 6 g/m.sup.2, most preferably not more than 4.5 g/m.sup.2.
The silver halide grains in the photosensitive material for prints are preferably silver chloride, silver chlorobromide or silver chlorobromoiodide grains comprising at least 95 molar % of silver chloride. Particularly, for the rapid process, substantially silver iodide-free silver chlorobromide or silver chloride can be preferably used. The term "substantially silver iodide-free" herein indicates that silver iodide content is not higher than 1 molar %, preferably not higher than 0.2 molar %. Further, in some cases, high-silver chloride grains containing 0.01 to 3 molar % of silver iodide on the emulsion surface as described in J. P. KOKAI No. Hei 3-84545 are preferably used so as to improve the high-intensity sensitivity, spectral sensitivity or storability of the photosensitive material. Although the halogen composition of the emulsion may be the same or different among the grains, the properties of all the grains can be easily made uniform by using an emulsion of grains having a uniform halogen composition. As for the halogen composition distribution in the silver halide grains in the emulsion, grains can be suitably selected from among those having a so-called homogeneous structure in which the composition in any part of the grain is uniform; those having a so-called laminated structure in which the halogen composition in the core of the silver halide grain is different from that in the shell (one or more layers) surrounding the core; and those having a structure which has a non-layer part having a different halogen composition in the core or on the surface (when such a ion-layer part is on the surface of the grain, the structure is such that the different composition part is conjugated with the edge, corner or surface of the grain). To obtain a high sensitivity, grains having either of the latter two structures are preferred to the grains of the homogeneous structure. Those of the latter structures are preferred also from the viewpoint of the pressure resistance. When the silver halide grains have such a structure, the boundary between the parts each having a different halogen composition may be clear or, on the contrary, it may be made unclear by forming mixed crystals from compositions different from each other. Further, the structure may be positively made such that the composition gradually changes within the grain.
In an emulsion having a high silver chloride content, the grains preferably have such a structure that silver bromide local phase in the form of a layer or non-layer is contained in the silver halide grain and/or on the surface thereof. As for the halogen composition in the local phase, silver bromide content is preferably at least 10 molar %, more preferably at least 20 molar %. The local phase can be in the grain, at an edge or corner of the grain surface or on the grain surface. In a preferred embodiment, the local phase is epitaxially grown at a corner of the grain.
It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of the developer replenisher. In such a case, an emulsion comprising substantially pure silver chloride, i.e. an emulsion having a silver chloride content of 98 to 100 molar %, is also preferably used.
The average grain size (number-average diameter of a circle having an area equal to that of the projected area of the grain) of the silver halide grains contained in the silver halide emulsion is preferably 0.1 to 2 .mu.m.
As for the grain size distribution, the coefficient of variation (calculated by dividing the standard deviation of the grain size distribution by the average grain size) is not higher than 20%, desirably not higher than 15%, and more desirably not higher than 10 Namely, the emulsion is so-called monodisperse emulsion. In order to obtain a wide latitude, this monodisperse emulsion is preferably blended in the same layer or it is applied to form an interlayer.
The silver halide grains in the photographic emulsion may be in a regular crystal form such as a cubic, tetradecahedral or octahedral form; an irregular crystal form such as spherical or plate form; or a complex crystal form thereof. They include also a mixture of various crystal forms. In the present invention, it is preferred that at least 50%, preferably at least 70% and more preferably at least 90%, of the grains have the regular crystal forms. An emulsion in which more than 50% (in terms of the projected area), based on the all grains, of tabular grains have an average aspect ratio (diameter of the corresponding circle/thickness) of at least 5, preferably at least 8, is suitably usable.
The localized silver halide grain phase or its substrate may contain a different metal ion or complex ion thereof. Preferred are those selected from among ions and complexes of metals of the Groups VIII and IIb in the Periodic table, and lead ion and thallium ion. The localized phase mainly contains an ion or complex ion of a metal selected from among iridium, rhodium and iron, and the substrate mainly contains an ion or complex ion of a metal selected from among osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron. The kind and concentration of the metal ion in the locallized phase may be different from those in the substrate. A combination of two or more kinds of these metals can also be used. It is particularly preferred that the iron and iridium compounds are in the silver bromide locallized phase.
The metal ion-donating compound is incorporated into the localized silver halide grain phase and/or the other part of the grain (substrate) by adding it to an aqueous gelatin solution to be used as the dispersion medium, to an aqueous halide solution, to an aqueous silver salt solution or to another aqueous solultion in the course of forming the silver halide grains; or by using the compound in the form of fine silver halide grains containing the metal ion and dissolving the fine grains.
The metal ion used in the present invention can be incorporated into the grains in the emulsion before, during or immediately after the formation of the grains. The time of the incorporation can be changed depending on the position of the metal ion in the grain.
The silver halide emulsion is usually chemically and spectrally sensitized.
The chemical sensitization is conducted with a chalcogen sensitizer (in particular, sulfur sensitization typified by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound or tellurium sensitization with a tellurium compound). A noble metal sensitization typified by gold sensitization and reduction sensitization can be conducted either separately or in combination of them. Compounds preferably used for the chemical sensitization are those described from the right lower column on page 18 to the right upper column on p. 22 of J. P. KOKAI No. Sho 62-215272.
The effect obtained by the constitution of the photosensitive material of the present invention is more remarkable than that obtained by using a high-silver chloride emulsion sensitized with gold. The emulsion used in the present invention is of a so-called surface latent image-type, wherein the latent image is formed mainly on the grain surface.
The silver halide emulsion can contain various compounds or precursors thereof so as to prevent the fogging during the production, storage or processing of the photosensitive material, or to stabilize the photographic properties. Preferred examples of these compounds are described on pages 39 to 72 of the above-mentioned J. P. KOKAI No. Sho 62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron-attractive group) described in European Patent No. 0447647 are also preferably used.
The spectral sensitization is conducted for the purpose of imparting a spectral sensitivity in a desired wavelength range to the emulsion for forming each layer of the photosensitive material.
The spectral sensitizing dyes used for the spectral sensitization in blue, green and red zones include, for example, those described in F. M. Harmer, Heterocyclic compounds--Cyanine dyes and related compounds (published by John Wiley & Sons �New York, London! in 1964). Examples of the preferred compounds and the spectral sensitization method are described from the right upper column, page 22 to page 38 of the above-mentioned J. P. KOKAI No. Sho 62-215272. As for the red-sensitive spectral sensitizing dyes for the silver halide grains having a high silver chloride content, spectral sensitizing dyes described in J. P. KOKAI No. Hei 3-123340 are very excellent in the stability, adsorption strength and dependence of the exposure on the temperature.
For the efficient spectral sensitization of the infrared zone, sensitizing dyes described from the left upper column, page 12 to the left lower column, page 21 of J. P. KOKAI No. Hei 3-15049; from the left lower column, page 4 to the left lower column, page 15 of J. P. KOKAI No. Hei 3-20730; from line 21, page 4 to line 54, page 6 of European Patent No. 0,420,011; from line 12, page 4 to line 33, page 10 of European Patent No. 0,420,012; European Patent No. 0,443,466 and U.S. Pat. No. 4,975,362 are preferably used.
The spectrosensitizing dye can be added to the emulsion in any stage of the preparation of the emulsion, which has been known to be suitable for the addition. Namely, this dye can be added in any of the following stages: before the formation of the grains of the silver halide emulsion, during the formation thereof, immediately after the formation of the grains and before the step of washing with water, before or during the chemical sensitization, immediately after the chemical sensitization and before the solidification of the emulsion by cooling, and during the preparation of the coating solution. The spectrosensitizing dye is usually added after the completion of the chemical sensitization and before the application of the coating solution. It is also possible to add the spectrosensitizing dye together with the chemical sensitizer to conduct the spectral sensitization and chemical sensitization at the same time as described in U.S. Pat. Nos. 3,628,969 and 4,225,666; to conduct the spectral sensitization prior to the chemical sensitization as described in J. P. KOKAI No. Sho 58-113928; and to add the spectrosensitizing dye before the completion of the precipitation of the silver halide grains to start the spectral sensitization. The spectrosensitizing dye can be added in portions as suggested in U.S. Pat. No. 4,225,666. Namely, a part of this dye is added prior to the chemical sensitization and the balance is added after the completion of the chemical sensitization. Thus, the addition can be conducted in any stage of the formation of the silver halide grains as in a method described in U.S. Pat. No. 4,183,756. It is particularly preferred to add the spectrosensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.
The amount of the spectrosensitizing dye is determined as occasion demands in a wide range of preferably 0.5.times.10.sup.-6 to 1.0.times.10.sup.-2 mol, more preferably 1.0.times.10.sup.-6 to 5.0.times.10.sup.-3 mol, per mol of the silver halide.
When a sensitizing dye having a spectral sensitivity particularly in the range of red zone to infrared zone is used in the present invention, the dye is preferably used in combination with a compound described from the right lower column, page 13 to the right lower column, page 22 of J. P. KOKAI No. Hei 2-157749. By using such a compound, the storability of the photosensitive material, stability of the process and supersensitizing effect can be specifically improved. It is particularly preferred to use the dye in combination with a compound of the general formula (IV), (V) or (VI) given in J. P. KOKAI No. Hei 2-157749. Such a compound is used in an amount of 0.5.times.10.sup.-5 to 5.0.times.10.sup.-2 mol, more preferably 5.0.times.10.sup.-5 to 5.0.times.10.sup.-3 mol, per mol of the silver halide. Thadvantageousl used in an amount of advantageously 0.1 to 10,000 mol, more advantageously 0.5 to 5,000 mol, per mol of the sensitizing dye.
A dye (particularly oxonol or cyanine dye) which can be decolored by the process as described on pages 27 to 76 of European Patent No. 0,337,490 A2 can be incorporated into the hydrophilic colloid layer for the purpose of preventing the irradiation or halation or improving the safety of the safelight.
Some of the water-soluble dyes impair the color separation or safety of the safelight when they are used in an increased amount. Preferred dyes usable without impairing the color separation are water-soluble dyes described in Japanese Patent Application Nos. Hei 03-310143, 03-310189 and 03-310139.
A colored layer which can be decolored by the process can be used in place of the water-soluble dye or in combination with this dye. The colored layer which can be decolored by the process may be directly brought into contact with the emulsion layer or, alternatively, it may be brought into contact with the emulsion layer via an intermediate layer containing a color-mixing preventing agent such as gelatin or hydroquinone. The colored layer is preferably positioned below (on the support side) the emulsion layer of a primary color similar to the color of the colored layer. It is possible to form a color layer corresponding to each primary color, or to form color layers corresponding to some of the primary colors. It is also possible to form a color layer corresponding to two or more primary color zones. As for the optical reflection density of the color layer, the optical density at a wavelength at which the highest optical density is attained in the wavelength range for the exposure (i.e. visible ray region of 400 to 700 nm in a usual exposure with a printer, or the wavelength of a scanning exposure light source in the scanning exposure) is preferably 0.2 to 3.0, more preferably 0.5 to 2.5, and particularly 0.8 to 2.0.
For forming the color layer, a method known in the art can be employed. The methods are, for example, a method wherein a dye in the form of solid fine particle dispersion such as a dye described from the right upper column, page 3 to page 8 of J. P. KOKAI No. Hei 2-282244 or a dye described from the right upper column, page 3 to the left lower column, page 11 of J. P. KOKAI No. Hei 3-7931 is incorporated into the hydrophilic colloid layer; a method wherein a cationic polylmer is mordanted with an anionic dye; a method wherein a dye is adsorbed on fine particles of a silver halide or the like and is thus fixed in the layer; and a method wherein colloidal silver is used as described in J. P. KOKAI No. Hei 1-239544. As the method wherein a fine powder of a dye is dispersed in the solid form, J. P. KOKAI No. Hei 2-308244 (see pages 4 to 13) discloses a method wherein a fine dye powder which is substantially water-insoluble at a pH of 6 or below and substantially water-soluble at a pH of 8 or above is used. The method wherein a cationic polymer is mordanted with an aniodic dye is described on pages 18 to 26 of J. P. KOKAI No. Hei 2-84637. Methods for producing colloidal silver used as a photoabsorbent are described in U.S. Pat. Nos. 2,688,601 and 3,459,563. Among these methods, a method wherein the fine dye powder is incorporated or a method wherein the colloidal silver is used is preferred.
Gelatin is advantageously used as the binder or protective colloid for the photosensitive materials. Other hydrophilic colloids can also be used either singly or in combination with gelatin. Preferred gelatin is a low-calcium gelatin having a calcium content of at most 800 ppm, more preferably at most 200 ppm. An antifungal agent as described in J. P. KOKAI No. Sho 63-271247 is preferably used in order to prevent the propagation of various fungi and bacteria in the hydrophilic colloid layer, since they deteriorate the image.
In the printer exposure of the photosensitive material for printing, a band stop filter described in U.S. Pat. No. 4,880,726 is preferably used for eliminating the photo-color-mixing and also for remarkably improving the color reproducibility.
After the completion of the exposure, the photosensitive material can be subjected to an ordinary color development process. To rapidly conduct the process, it is preferred to conduct bleach-fixing after the color development. Particularly when the above-described high-silver chloride emulsion is used, pH of the bleach-fixing solution is preferably not higher than about 6.5, particularly not higher than about 6, for accelerating the desilverization.
The photographic additives usable herein are also mentioned in RD, and the corresponding portions are shown in the following table:
______________________________________Additive RD 17643 RD 18716 RD 307105______________________________________1. Chemical p. 23 p. 648, right p. 866 sensitizer column2. Sensitivity p. 648, right improver column3. Spectral pp. 23 to 24 p. 648, right pp. 866 to 868 sensitizer and colum to p. 649, supersensitizer right column4 Brightening p. 24 p. 647, right p. 868 agent column5. Light absorber, pp. 25 to 26 p. 649, right p. 873 filter, dye and column to p. 650, UV absorber left column6. Binder p. 26 p. 651, left pp. 873 to 874 column7. Plasticizer p. 27 p. 650, right p. 876 and lubricant column8. Coating aid pp. 26 and 27 p. 650, right pp. 875 to 876 and surfactant column9. Antistatic p. 27 p. 650, right pp. 876 to 877 agent column10. Matting agent pp. 878 to 879______________________________________
The photosensitive material can contain various dye-forming couplers. Among them, the following couplers are particularly preferred:
Yellow couplers: couplers represented by formulae (I) and (II) in EP 502,424A; those of formulae (I) and (II) in E.P. No. 513,496A (particularly Y-28 on page 18); those of general formula (I) in Claim 1 of Japanese Patent Application No. Hei 4-134523; those of general formula (I) in lines 45 to 55, column 1 of U.S. Pat. No. 5,066,576; those of general formula (I) in paragraph 0008 of J. P. KOKAI No. Hei 4-274425; those set forth in Claim 1, on p. 40 of E. P. No. 498,381A1 �particularly D-35 on p. 18); those of formula (Y) on p. 4 of E. P. No. 447,969A1 (particularly Y-1 on p. 17 and Y-54 on p. 41); and those of general formulae (II) to (IV) in lines 36 to 58, column 7 of U.S. Pat. No. 4,476,219 (particularly II-17, 19 (column 17) and II-24 (column 19)!,
Acylacetanilide couplers: particularly pivaloylacetanilide couplers having a halogen atom or alkoxyl group at the o-position of the anilide ring; acylacetanilide couplers wherein the acyl group is a cycloalkanecarbonyl group having a substituent at the 1-position as described in E. P. No. 0,447,969A and J. P. KOKAI Nos. Hei 5-107701 and 5-113642; and malondianilide couplers described in E. P. Nos. 0,482,552A and 0,524,540A,
Magenta couplers: those described in J. P.KOKAI No. Hei 3-39737 �L-57 (right lower column, p. 11), L-68 (right lower column, p. 12) and L-77 (right lower column, p. 13); �A-4!-63 (p. 134), �A-4!-73 and 75 (p. 139) of E. P. No. 456,257; M-4 and 6 (p. 26) and M-7 (p. 27) of E. P. No. 486,965; M-45 in paragraph 0024 of Japanese Patent Application No. Hei 4-234120; M1 in paragraph 0036 of Japanese Patent Application No. Hei 4-36917; and M-22 in paragraph 0237 of J. P. KOKAI No. Hei 4- 362631,
5-Pyrazolone magenta couplers: those of arylthio-linked coupling-off type described in W.O. 92/18901, 92/18902 and 92/18903,
Pyrazoloazole couplers: those containing a sulfonamido group in the molecule as described in J. P. KOKAI No. Sho 61-65246; those having an alkoxyphenylsulfonamido ballast group as described in J. P. KOKAI No. Sho 61-147254; and those having an alkoxy or aryloxy group at the 6-position as described in European Patent Nos. 226,849A and 294,785A,
Cyan couplers: CX-1, 3, 4, 5, 11, 12, 14 and 15 (pp. 14 to 16) of J. P. KOKAI No. Hei 4-204843; C-7 and 10 (p. 35), 34 and 35 (p. 37) ,,(I-1) and (I-17) (pp. 42 to 43) of J. P. KOKAI No. Hei 4-43345; and those of general formula (Ia) or (Ib) in Claim 1 of Japanese Patent Application No. Hei 4-236333 ,
Polymer couplers: P-1 and P-5 (p. 11) of J. P. KOKAI No. Hei 2-44345, and
Phenol couplers and naphthol couplers; diphenylimidazole cyan couplers described in J. P. KOKAI No. Hei 2-33144; 3-hydroxypyridine cyan couplers described in E. P. No. 0,333,185A2; cyclic active methylene cyan couplers described in J. P. KOKAI No. Sho 64-32260; pyrrolopyrazole cyan couplers described in E. P. No. 0,456,226A1; pyrroloimidazole cyan couplers described in E. P. No. 0,484,909; and pyrrolotriazole cyan couplers described in E. P. Nos. 0488,248 and 0,491,197A1.
The couplers capable of forming a colored dye having a suitable diffusibility are preferably those described in U.S. Pat. No. 4,366,237, G.B. Patent No. 2,125,570, E. P. No. 96,873B and DE P. No. 3,234,533.
The couplers used for compensation for unnecessary absorption of the colored dye are preferably as follows: yellow-colored cyan couplers of formulae (CI), (CII), (CIII) and (CIV) on p. 5 of E. P. No. 456,257A1 (particularly YC-86 on p. 84); yellow-colored magenta coupler ExM-7 (p. 202), EX-1 (p. 249) and EX-7 (p. 251) described in E. P. No. 456,257A1; magenta-colored cyan coupler CC-9 (column 8) and CC-13 (column 10) described in U.S. Pat. No. 4,833,069; couplers (2) (column 8) in U.S. Pat. No. 4,837,136; and colorless masking couplers of formula (A) in Claim 1 of WO 92/11575 (particularly compounds given on pages 36 to 45).
Compounds (including couplers) capable of reacting with an oxidation product of the developing agent to form a photographically useful compound residue are as follows: development inhibitor-releasing compounds such as compounds of formulae (I), (II), (III) and (IV) on page 11 of E. P. No. 378,236A1 �particularly compounds T-101 (p. 30), T-104 (p. 31), T-113 (p. 36), T-131 (p. 45), T-144 (p. 51) and T-158 (p. 58)!, compounds of formula (I) on page 7 of E. P. No. 436,938A2 �particularly D-49 (p. 51)!, compounds of formula (1) in Japanese Patent Application No. Hei 4-134523 �particularly (23) in paragraph 0027!, compounds of formulae (I), (II) and (III) on pages 5 to 6 of E. P. No. 440,195A2 �particularly I-(1) on page 29!; bleaching accelerator-releasing compounds such as compounds of formulae (I) and (I') on page 5 of E. P. No. 310,125A2 �particularly (60) and (61) on p. 61! and compounds of formula (I) in Claim 1 of Japanese Patent Application No. Hei 4-325564 �particularly (7) in paragraph 0022!; ligand-releasing compounds such as those of LIG-X in Claim 1 of U.S. Pat. No. 4,555,478 (particularly compounds in lines 21 to 41 in column 12); leuco dye-releasing compounds such as compounds 1 to 6 in columns 3 to 8 of U.S. Pat. No. 4,749,641; fluorescent dye-releasing compounds such as compounds represented by COUP-DYE in Claim 1 of U.S. Pat. No. 4,774,181 (particularly compounds 1 to 11 in columns 7 to 10); development accelerator- or fogging agent-releasing compounds such as those of formulae (1), (2) and (3) in U.S. Pat. No. 4,656,123 �particularly (I-22) in column 25! and ExZK-2 in lines 36 to 38 on page 75 of E. P. No. 450,637A2; compounds which do not release a dye-forming group before coupling-off such as compounds of formula (I) in Claim 1 of U.S. Pat. No. 4,857,447 (particularly Y-1 to Y-19 in columns 25 to 36).
As additives other than the couplers, those described below are preferred.
Dispersion medium for oil-soluble organic compounds: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86 and 93 (pp. 140 to 144) described in J. P. KOKAI No. Sho 62-215272; latices for impregnation of oil-soluble organic compounds: latices described in U.S. Pat. No. 4,199,363; oxidized developing agent scavengers: compounds of formula (I) in lines 54 to 62, column 2 of U. S. Pat. No. 4,978,606 �particularly 1-(1), (2), (6) and (12) in columns 4 and 5! and those of formulae in lines 5 to 10, column 2 of U.S. Pat. No. 4,923,787 �particularly compound 1 (column 3)!; antistaining agents: those of formulae (I) to (III) in lines 30 to 33, p. 4 of E. P. No. 298,321A, particularly 1-47, 72, III-1 and 27 (pp. 24 to 48); discoloration inhibitors: A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94 and 164 of E. P. No. 298,321A (pp. 69 to 118), II-1 to III-23 in columns 25 to 38 of U.S. Pat. No. 5,122,444, particularly III-10, I-1 to III-4 on pp. 8 to 12 of E. P. No. 471,347A, particularly II-2, and A-1 to 48 in columns 32 to 40 of U.S. Pat. No. 5,139,931, particularly A-39 and 42; materials capable of reducing the amount of dye formation enhancer or color mixing-inhibitor used: I-1 to II-15 on pp. 5 to 24 of E. P. No. 411,324A, particularly 1-46; formalin scavengers: SCV-1 to 28 on pp. 24 to 29 of E. P. No. 477,932A, particularly SCV-8; hardeners: H-1, 4, 6, 8 and 14 on p. 17 of J. P. KOKAI No. Hei 1-214845, and compounds (H-1 to 54) of formulae (VII) to (XII) in columns 13 to 23 of U.S. Pat. No. 4,618,573, compounds (H-1 to 76) of formula (6) in the right, lower part on p. 8 of J. P. KOKAI No. Hei 2-214852, particularly H-14, and compounds set forth in Claim 1 of U.S. Pat. No. 3,325,287; development inhibitor precursors: P-24, 37 and 39 (pp. 6 and 7) of J. P. KOKAI No. Sho 62-168139; and compounds set forth in Claim 1 of U.S. Pat. No. 5,019,492, particulrly 28 and 29 in column 7; antiseptics and mildew-proofing agents: I-1 to III-43 in columns 3 to 15 of U.S. Pat. No 4,923,790, particularly II-1, 9, 10, 18 and III-25; stabilizers and antifoggants: I-1 to (14) in columns 6 to 16 of U.S. Pat. No. 4,923,793, particularly I-1, 60, (2) and (13), and compounds 1 to 65 in columns 25 to 32 of U.S. Pat. No. 4,952,483, particularly 36; chemical sensitizers: triphenylphosphine selenide and compound 50 of J. P. KOKAI No. Hei 5-40324; dyes: a-1 to b-20 on pp. 15 to 18 of J. P. KOKAI No. Hei 3-156450, particularly a-1, 12, 18, 27, 35, 36 and b-5, V-1 to 23 on pp. 27 to 29, particularly V-1, F-I-1 to F-II-43 on pp. 33 to 55 of E. P. No. 445,627A, particularly F-1-11 and F-II-8, III-1 to 36, on pp. 17 to 28 of E. P. No. 457,153A, particularly III-1 and 3, fine crystal dispersions of Dye-1 to 124 on pp. 8 to 26 of WO88/04794, compounds 1 to 22 on pp. 6 to 11 of E. P. No. 319,999A, particularly compound 1, compounds D-1 to 87 of formulae (1) to (3) (pp. 3 to 28) of E. P. No. 519,306A, compounds 1 to 22 (columns 3 to 10) of formula (I) in U.S. Pat. No. 4,268,622, and compounds (1) to (31) of formula (I) (columns 2 to 9) of U.S. Pat. No. 4,923,788; and UV absorbers: compounds (18b) to (18r) of formula (1) and 101 to 427 (pp. 6 to 9) of J. P. KOKAI No. 46-3335, compounds (3) to (66) (pp. 10 to 44) of formula (I), compounds HBT-1 to 10 (p. 14) of formula (III) of E. P. No. 520,938A, and compounds (1) to (31) of formula (1) (columns 2 to 9) of E. P. No. 521,823A.
The support used for the photosensitive material for printing may be made of any material such as a glass, paper or plastic film so far as the photographic emulsion layer can be applied thereto. The most preferred is a support of reflection type.
The term "support of reflection type" herein indicates a support having a high reflectivity so as to obtain a clear dye image in the silver halide emulsion layer. The supports of this type include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate dispersed therein, and those comprising the hydrophobic resin per se containing the light-reflecting substance. The supports include, for example, a polyethylene-coated paper, polyethylene terephthalate-coated paper, synthetic polypropylene paper, transparent support having a reflective layer or containing a reflective substance, such as a glass plate, a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate film, polyamide film, polycarbonate film, polystyrene film and vinyl chloride resin film. The preferred supports of reflection type used in the present invention are paper supports the both surfaces of which are each coated with a water-resistant resin layer, wherein at least one of the water-resistant resin layers contains fine white pigment particles.
The water-resistant resins used for forming the reflective support are those having a water absorption of not higher than 0.5% by weight, preferably not higher than 0.1% by weight. They include polyolefins such as polyethylene, polypropylene and other ethylene polymers; vinyl polymers and copolymers thereof such as polystyrene, polyacrylate and copolymers of them; and polyesters such as polyethylene terephthalate and polyethylene isophthalate and copolymers thereof. Particularly preferred are polyethylene and polyesters.
The polyethylenes usable herein are high-density polyethylene, low-density polyethylene, linear low-density polyethylene and blends of these polyethylenes. These polyethylene resins preferably have a melt flow rate (hereinafter referred to as "MFR") in the range of 1.2 to 12 g/10 min as determined under conditions 4 in Table 1 of JIS K 7210 before processing. The term "MFR of polyolefin resin before processing" herein indicates MFR of the resin before blending it with a blueing agent or white pigment.
The weight mixing ratio of the water-resistant resin to the white pigment is 98/2 to 30/70, preferably 95/5 to 50/50 and more preferably 90/10 to 60/40. When the white pigment content is below 2% by weight, a sufficient degree of whiteness cannot be obtained and, on the contrary, when it exceeds 70% by weight, the surface smoothness is insufficient for forming the photographic support having a high gloss.
The water-resistant resin layer formed on the support has a thickness of preferably 2 to 200 .mu.m, and more preferably 5 to 80 .mu.m. When it is above 200 .mu.m, problems of the properties of the resin such as cracking due to an increase of the brittleness of the resin are caused. On the other hand, when it is below 2 .mu.m, the water proofness which is the essential purpose of coating is insufficient and, in addition, satisfactory degree of whiteness and surface smoothness cannot be obtained at the same time, and the layer becomes too much soft unfavorably.
The thickness of the resin or resin composition layer coating the backside (the side opposite to the photosensitive layer-forming side) of the support is preferably 5 to 100 .mu.m, more preferably 10 to 50 .mu.m. When the thickness is above this range, problems of the properties of the resin such as cracking due to an increase of the brittleness of the resin are caused. When the thickness is below this range, the water proofness which is the essential purpose of coating is insufficient and, in addition, the layer becomes too much soft unfavorably.
From the viewpoints of the cost, producibility, etc. of the reflective support, it is preferred in some cases that photosensitive layer-side of the support is coated with two or more water-resistant resin layers each having a different white pigment content. In this case, among the water-resistant resin coating layers having different white pigment contents, the white pigment content of a water-resistant resin coating layer most close to the support is lower than that of one or more water-resistant resin coating layers formed thereon. In a more preferred embodiment, the reflective support has two or more water-resistant resin coating layers each having a different white pigment content, in which the water-resistant resin coating layer most close to the photosensitive layer has the highest white pigment content. In another preferred embodiment, the reflective support has at least three water-resistant resin coating layers, in which one or more intermediate layers (interposed between that most close to the photosensitive layer and that most close to the support) have the highest white pigment content.
Each of the water-resistant resin layers has a white pigment content of 0 to 70% by weight, preferably 0 to 50% by weight and more preferably 0 to 40% by weight. Among the water-resistant resin layers, a layer having the highest white pigment content contains 9 to 70% by weight, preferably 15 to 50% by weight and still preferably 20 to 40% by weight, of the white pigment. When the white pigment content of this layer is below 9% by weight, the sharpness of the image is poor and, on the contrary, when it is above 70% by weight, cracks are formed in a melt-extruded film.
The thickness of each of the multiple water-resistant resin layers is preferably 0.5 to 50 .mu.m. For example, when the support has two water-resistant resin layers, the thickness of each layer is preferably 0.5 to 50 .mu.m and the total layer thickness is preferably in the above-described range (2 to 200 .mu.m). When the support has three such layers, it is preferred that the thickness of the top layer is 0.5 to 10 .mu.m, that of the intermediate layer is 5 to 50 .mu.m and that of the bottom layer (the layer the closest to the support) is 0.5 to 10 .mu.m. When the thickness of the top or bottom layer is below 0.5.mu.m, die slip lines are easily formed by the effect of the white pigment contained in the intermediate layer in a high concentration. On the other hand, when the thickness of the top layer or the bottom layer, particularly the top layer, is above 10 .mu.m, the sharpness is reduced.
The fine white pigment particles are preferably homogeneously dispersed in the reflective layer without forming masses of the particles. The degree of distribution can be determined by determination of the rate (%) of area (Ri) occupied by the fine particles projected in a unit area. The coefficient of variation of the rate of occupied area (%) can be determined as the ratio of the standard deviation (s) of Ri to the average (R) of Ri, i.e. s/R. The coefficient of variation (%) of the fine pigment particles is preferably not above 0.15, more preferably not above 0.12 and particularly not above 0.08 in the present invention.
A support having a secondary diffuse-reflective surface can also be used. The term "secondary diffuse reflectivity" indicates a diffuse reflectivity realized by making the surface having a mirror plane rough to divide the surface into fine mirror planes facing different directions so that the faces of the finely divided surface (mirror planes) are dispersed. As for the roughness of the secondary diffuse- reflective surface, the average three-dimensional roughness, based on the central face is 0.1 to 2 .mu.m, preferably 0.1 to 1.2 .mu.m. The surface roughness frequency for a roughness of at least 0.1 .mu.m is preferably 0.1 to 2,000 cycles/mm, more preferably 50 to 600 cycles/mm. The details of such a support are described in J. P. KOKAI No. Hei 2-239244.
The supports suitable for the photosensitive material are described, for example, on page 28 of the above-described RD. 17643; from right column, page 647 to left column, page 648 of RD. 18716; and on page 879 of RD 307105.
The photosensitive material for the photography has a total thickness of the hydrophilic colloidal layers on the emulsion layer-side of 23 .mu.m or below, preferably 20 .mu.m or below, and particularly 13 to 17 .mu.m. The film-swelling rate T.sub.1/2 is preferably 5 to 15 seconds. T.sub.1/2 is defined to be the time required for attaining the thickness of a half (1/2) of the saturated film thickness, the saturated film thickness being 90% of the maximum thickness of the film swollen with the color developer at 30.degree. C. for 3 minutes and 15 seconds. The film-swelling rate T.sub.1/2 can be controlled by adding a hardener to gelatin used as the binder or by varying the time conditions after the coating. The swelling rate is preferably 150 to 350%. The swelling rate can be calculated from the maximum thickness of the swollen film obtained under the above-described conditions by the following formula:
�(Maximum thickness of swollen film)-(film thickness)!/(film thickness).
The photosensitive material can have a hydrophilic colloid layer (in other words, back layer) having a total thickness of 2 to 20 .mu.m on dry basis on the opposite side to the emulsion layer. The back layer preferably contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surfactant, etc. The swelling rate of the back layer is preferably 150 to 500%.
The photosensitive materials preferably used in the present invention are those described below.
The photosensitive materials preferably used herein are those having a magnetic recording layer which comprises magnetic particles (preferably ferromagnetic iron oxide particles coated with Co, and the like) dispersed in a binder. The recording layer is preferably optically transparent and covers the whole surface of the photosensitive material. The magnetic particles may be treated with a coupling agent as described in J. P. KOKAI No. Hei 6-161032. Polymers described in, for example, J. P. KOKAI No. Hei 4-219569 are preferably used as the binder. Although the recording layer may be formed in any part of the support, it is preferably formed on the opposite side (back layer) of the support to the emulsion layer. Preferably, a layer containing a lubricant is formed on the recording layer and a matting agent is contained in the outmost photosensitive emulsion layer on the support.
The photosensitive material preferably contains an antistatic agent so that is still has the antistatic properties even after the development process. Preferred antistatic agents are electroconductive metal oxides and ionic polymers. The antistatic agent is preferably used so as to obtain an electric resistance of 10.sup.12 .OMEGA..cm or less at a temperature of 25.degree. C. and RH of 10%.
The photosensitive materials having the magnetic recording layer are described in U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259 and 5,215,874 and EP 466,130A.
The support for the photosensitive material is preferably a thin layer of a polyester having no rolling properties. The thickness of the support is 50 to 105 .mu.m, and the main material therefor is preferably a polyethylene aromatic dicarboxylate polyester (particularly a polyester produced mainly from benzenedicarboxylic acid or naphthalenedicarboxylic acid and ethylene glycol). The support has a glass transition temperature of preferably 50.degree. to 200.degree. C. The surface of the support is processed by ultraviolet irradiation, corona discharge, glow discharge or flaming. The support is preferably heat-treated at a temperature in the range of 40.degree. C. to the glass transition temperature of the support for 0.1 to 1,500 hours before or after the formation of the subbing layer and before the formation of the emulsion layer. The support as well as photosensitive material, development process and cartridge are described in Kokaigiho, Kogi No. 94-6023 �published by Hatsumei Kyokai (Japan Institute of Invention and Innovation) in 1994!.

�EXAMPLES!
The following Examples will further illustrate the present invention, which by no means limit the invention.
Example 1
Preparation of multi-layer color photosensitive material:
A multilayer color photosensitive material, which will be referred to as "sample 101", was prepared by forming layers of the following compositions:
(Compositions of photosensitive layers)
Main materials to be used for forming the layers are classified as follows:
ExC: cyan coupler
ExM: magenta coupler
ExY: yellow coupler
ExS: sensitizing dye
UV: ultraviolet absorber
HBS: high-boiling organic solvent
H: gelatin hardener
The numerals for the respective components indicate the amount of coating given by g/m.sup.2. Those for silver halides are given in terms of silver. Those for sensitizing dyes are given in terms of molar unit per mol of the silver halide contained in the same layer.
(Sample 101)
______________________________________The first layer (antihalation layer):black colloidal silver silver 0.18glatin 1.60ExM-1 0.11ExF-1 3.4 .times. 10.sup.-3ExF-2 (solid dispersed dye) 0.03ExF-3 (solid dispersed dye) 0.04HBS-1 0.16The second layer (intermediate layer):ExC-2 0.055UV-1 0.011UV-2 0.030UV-3 0.053HBS-1 0.05HBS-2 0.02polyethyl acrylate latex 8.1 .times. 10.sup.-2gelatin 1.75The third layer (low-speed red-sensitive emulsionlayer)silver bromoiodide emulsion A silver 0.46ExS-1 5.0 .times. 10.sup.-4ExS-2 1.8 .times. 10.sup.-5ExS-3 5.0 .times. 10.sup.-4ExC-1 0.16ExC-3 0.045ExC-5 0.0050ExC-7 0.001ExC-8 0.010Cpd-2 0.005HBS-1 0.090gelatin 0.87The fourth layer (medium-speed red-sensitiveemulsion layer)silver bromoiodide emulsion D silver 0.70ExS-1 3.0 .times. 10.sup.-4ExS-2 1.2 .times. 10.sup.-5ExS-3 4.0 .times. 10.sup.-4ExC-1 0.22ExC-2 0.055ExC-5 0.007ExC-8 0.009Cpd-2 0.036HBS-1 0.11gelatin 0.70The fifth layer (high-speed red-sensitive emulsionlayer)silver bromoiodide emulsion E silver 1.62ExS-1 2.0 .times. 10.sup.-4ExS-2 1.0 .times. 10.sup.-5ExS-3 3.0 .times. 10.sup.-4ExC-1 0.133ExC-3 0.040ExC-6 0.040ExC-8 0.014Cpd-2 0.050HBS-1 0.22HBS-2 0.10gelatin 0.85The sixth layer (intermediate layer)Cpd-1 0.07HBS-1 0.04polyethyl acrylate latex 0.19gelatin 2.30The seventh layer (low-speed green-sensitiveemulsion layer)silver bromoiodide emulsion A silver 0.24silver bromoiodide emulsion B silver 0.10silver bromoiodide emulsion C silver 0.14ExS-4 4.0 .times. 10.sup.-5ExS-5 1.8 .times. 10.sup.-4ExS-6 6.5 .times. 10.sup.-4ExM-1 0.005ExM-2 0.30ExM-3 0.09ExY-1 0.015HBS-1 0.26HBS-3 0.006gelatin 0.80The eighth layer (medium-speed green-sensitiveemulsion layer)silver bromoiodide emulsion D silver 0.94ExS-4 2.0 .times. 10.sup.-5ExS-5 1.4 .times. 10.sup.-4ExS-6 5.4 .times. 10.sup.-4ExM-2 0.16ExM-3 0.045ExY-1 0.008ExY-5 0.030HBS-1 0.14HBS-3 8.0 .times. 10.sup.-3gelatin 0.90The ninth layer (high-speed green-sensitiveemulsion layer)silver bromoiodide emulsion E silver 1.29ExS-4 3.7 .times. 10.sup.-5ExS-5 8.1 .times. 10.sup.-5ExS-6 3.2 .times. 10.sup.-4ExC-4 0.11ExM-1 0.016ExM-4 0.046ExM-5 0.023Cpd-3 0.050HBS-1 0.20HBS-2 0.08polyethyl acrylate latex 0.26gelatin 0.82The tenth layer (yellow filter layer)yellow colloidal silver silver 0.010Cpd-1 0.10ExF-5 (solid dispersed dye) 0.06ExF-6 (solid dispersed dye) 0.06ExF-7 (oil-soluble dye) 0.005HBS-1 0.055gelatin 0.70The eleventh layer (low-speed blue-sensitiveemulsion layer)silver bromoiodide emulsion A silver 0.25silver bromoiodide emulsion C silver 0.25silver bromoiodide emulsion D silver 0.10ExS-7 8.0 .times. 10.sup.-4ExY-1 0.010ExY-2 0.70ExY-3 0.055ExY-4 0.006ExY-6 0.075ExC-7 0.040HBS-1 0.25gelatin 1.60The twelfth layer (high-speed blue-sensitiveemulsion layer)silver bromoiodide emulsion F silver 1.30ExS-7 3.0 .times. 10.sup.-4ExY-2 0.15ExY-3 0.06HBS-1 0.070gelatin 1.13The thirteenth layer (the first protective layer)UV-2 0.08UV-3 0.11UV-4 0.26HBS-1 0.09gelatin 1.20The fourteenth layer (the second protective layer)silver bromoiodide emulsion G silver 0.10H-1 0.30B-1 (diameter: 1.7 .mu.m) 5.0 .times. 10.sup.-2B-2 (diameter: 1.7 .mu.m) 0.10B-3 0.10S-1 0.20gelatin 1.75______________________________________
Further, the respective layers suitably contain W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salts, lead salts, gold salts, platinum salts, iridium salts, palladium salts and rhodium salts in order to improve the storability, processability, pressure resistance, mildew-proofing and bacteria-proofing properties, antistatic properties and coating easiness.
TABLE 1__________________________________________________________________________ Average Rate of Average Coeffi cient of grains having AgI grain variation diameter/thick-Emul- content diameter of grain ness ratio of Grain structure/sion (%) (.mu.m) diameter (%) at least 2 (%) shape__________________________________________________________________________A 2.1 0.55 25 81 homogeneous structure, tabularB 9.1 0.63 26 84 triple structure, tabularC 3.1 0.60 24 98 triple structure, tabularD 4.2 0.80 19 92 triple structure, tabularE 3.2 1.10 17 96 triple structure, tabularF 10.8 1.75 27 60 double structure, tabularG 1 0.07 15 0 homogeneous structure, cubic__________________________________________________________________________ In Table 1: (1) The emulsions A to F were reductionsensitized with thiourea dioxide and thiosulfonic acid in the step of preparation of the grains as described in an Example of J. P. KOKAI No. Hei 2191938. (2) The emulsions A to F were sensitized by gold sensitization, sulfur sensitization and selenium sensitization methods in the presence of a spectral sensitizing dye mentioned above for each photosensitive layer an sodium thiocyanate as described in an Example of J. P. KOKAI No. Hei 3237450. (3) In the preparation of tabular grains, a lowmolecular weight gelatin was used as described in an Example of J. P. KOKAI No. Hei 1158426. (4) Dislocation lines as described in J. P. KOKAI No. Hei 3237450 were obserbed on the tabular grains with a highvoltage electron microscope.
Preparation of dispersion of organic solid disperse dye:
ExF-2 which will be described below was dispersed as follows: 21.7 ml of water, 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethanesulfonate and 0.5 g of 5% aqueous solution of p-octylphenoxy polyoxyethylene ether (degree of polymerization: 10) were fed into a 700 ml pot mill. 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added thereto, and the mixture was milled with a BO type vibration ball mill (a product of Chuo Koki) for 2 hours to obtain a dispersion. Then the dispersion was taken out and added to 8 g of 12.5% aqueous gelatin solution. The beads were removed by filtration to obtain a dispersion of the dye in gelatin. The average grain diameter of the fine dye grains was 0.44 .mu.m.
A solid dispersion of each of ExF-3, ExF-4 and ExF-6 was obtained in the same manner as that described above. The average grain diameters of the fine dye grains were 0.24 .mu.m, 0.45 .mu.m and 0.52 .mu.m, respectively. ExF-5 was dispersed by a microprecipitation dispersion method described in Example 1 in E. P. No. 0,549,489 A. The average grain diameter was 0.06 .mu.m. ##STR7##
______________________________________(Processing step) Process Process Amount of CapacityStep time temp. replenisher* of tank, l______________________________________Color development 3 min 40.0.degree. C. 200 ml 2.0Bleaching 30 sec 45.0.degree. C. 130 ml 0.7Fixing (1) 30 sec 45.0.degree. C. 100 ml 0.7Fixing (2) 30 sec 45.0.degree. C. 70 ml 0.7Washing with water (1) 15 sec 45.0.degree. C. -- 0.4Washing with water (2) 15 sec 45.0.degree. C. -- 0.4Washing with water (3) 15 sec 45.0.degree. C. 400 ml/m.sup.2 0.4Drying 20 sec 80.degree. C.______________________________________ *The amount of the replenisher is given per m.sup.2 of the photosensitive material. (The steps ranging from the washing with water (3) to the fixin (2) were conducted with four tanks by countercurrent multistage cascade method.) (The steps ranging from the fixing (2) to fixing (1) were conducted with two tanks by countercurrent multistage cascade method.)
The description will be made on the composition of each solution:
______________________________________ Mother(Color developer) liquid Replenisher______________________________________Diethylenediaminetetraacetic acid 4.0 g 4.0 gSodium 4,5-dihydroxybenzene-1,3- 0.5 g 0.5 gdisulfonateSodium sulfite 3.9 g 6.5 gPotassium carbonate 37.5 g 39.0 gPotassium bromide 2.7 g --Potassium iodide 1.3 mg --N-Methylhydroxylamine hydrochloride 4.5 g 5.5 g2-Methyl-4-�N-ethyl-N-.beta.-hydroxyethyl)- 5.0 g 9.0 gamino!aniline sulfate (P-5)Water ad 1000 ml 1000 mlpH (adjusted with potassium hydroxide 10.05 10.25and sulfuric acid)______________________________________ Mother(Bleaching solution) liquid Replenisher______________________________________Ferric ammonium 1,3-diaminopropanetetra- 0.33 mol 0.50 molacetate monohydrateFerric nitrate nonahydrate 0.30 mol 4.5 molAmmonium bromide 0.80 mol 1.20 molAmmonium nitrate 0.20 mol 0.30 molAcetic acid 0.67 mol 1.0 molWater ad 1000 ml 1000 mlpH (adjusted with ammonia water) 4.5 4.0______________________________________ (common to the mother(Fixing solution) liquid and replenisher) (g)______________________________________Ammonium sulfite 28Aqueous ammonium thiosulfate (700 g/l) 280 mlImidazole 15Ethylenediaminetetraacetic acid 15Water 1.0 lpH (adjusted with ammonia water and 5.8acetic acid)______________________________________
(Washing water) (common to the mother liquid and replenisher)
Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B; a product of Rohm & Haas Co.) and an OH-type artion exchange resin (Amberlite IR-400; a product of Rohm & Haas Co.) to reduce calcium and magnesium ion concentration to 3 mg/l or below, and then 20 mg/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were added to the water. The pH of the water was in the range of 6.5 to 7.5.
______________________________________ (common to the mother(Stabilizer) liquid and replenisher)______________________________________1,2-Benzoylisothiazoline-3-on 0.1Polyoxyethylene-p-monononylphenyl ether 0.2(average degree of polymerization: 10)Water ad 1.0 lpH (adjusted with ammonia water and 8.50.hydrochloric acid)______________________________________
After image-exposure of the sample 101, the continuous process was conducted until the amount of the replenished bleach fixing solution had become three times as much as the amount of the mother liquid.
The running processing solution thus obtained will be referred to as processing solution 201. Then the color developer was prepared in the same manner as above except that the color developing agent P-5 sulfate in the color developer was replaced with an equal molar amount of a comparative color developing agent or the color developing agent of the present invention as shown in Table 2, and the same continuous process as that described above was conducted to obtain running processing solutions (processing solutions 202 to 210).
The rapidness of the process was determined as follows. After the wedge exposure of the sample 101, it was processed �running process step (a)! with a running processing solution (processing solutions 202 to 210) while the color development period was changed from 1 minute to 3 minutes at intervals of 10 seconds. The optical densities of the yellow, magenta and cyan images of each of the resultant samples were determined. Then, after the wedge-exposure of the sample 101 conducted in the same manner as that described above, it was processed in comparative developing steps (b) described below, and the optical densities of the yellow, magenta and cyan images were determined in the same manner as that described above. The density curve of the magenta image obtained in the comparative developing step (b) was compared with that of each sample (obtained at intervals of 10 seconds as described above), and the processing time in which the equal or higher magenta density was obtained was measured to obtain the results shown in Table 2.
Then the degree of lowering of the density of each of the yellow and cyan images was determined by using a sample which necessitated an equal processing time for obtaining the same magenta density. The yellow and cyan densities of each sample were determined with such an exposure that magenta density of 2.0 would be obtained. The densities �minus (-) means lowering of the density and plus (+) means increase thereof! are given in Table 2 as compared with the yellow and cyan densities obtained in the comparative developing steps (b). Comparative color developing agent: ##STR8##
______________________________________Comparative development steps (b)(Processing method)Step Time Temp.______________________________________Color development 3 min 15 sec 38.degree. C.Bleaching 1 min 00 sec 38.degree. C.Bleach-fixing 3 min 15 sec 38.degree. C.Washing with water (1) 40 sec 35.degree. C.Washing with water (2) 1 min 00 sec 35.degree. C.Stabilization 40 sec 38.degree. C.Drying 1 min 15 sec 55.degree. C.______________________________________
The composition of each of the processing solutions was as follows:
______________________________________ (Unit: g)______________________________________(Color developer)Diethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-1,1-diphosphonic acid 2.0Sodium sulfite 4.0Potassium carbonate 30.0Potassium bromide 1.4Potassium iodide 1.5 mgHydroxylamine sulfate 2.44-�N-ethyl-N-(.beta.-hydroxyethyl)amino!-2-methyl- 4.5aniline sulfate �P-5!Water ad 1.0 lpH (with potassium hydroxide and sulfuric acid) 10.05(Bleaching bath)Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0Disodium ethylenediaminetetraacetate 10.0Ammonium bromide 100.0Ammonium nitrate 10.0Bleaching accelerator 0.005 mol(CH.sub.3).sub.2 N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2--N(CH.sub.3).sub.2.2HClAmmonia water (27%) 15.0 mlWater ad 1.0 lpH (adjusted with ammonia water and nitric acid) 6.3(Bleach-fixing bath)Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0Disodium ethylenediaminetetraacetate 5.0Sodium sulfite 12.0Aqueous ammonium thiosulfate solution (700 g/l) 240.0 mlAmmonia water (27%) 6.0 mlWater ad 1.0 lpH (adjusted with ammonia water and acetic acid) 7.2______________________________________
(Washing water)
Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B; a product of Rohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400; a product of Rohm & Haas Co.) to reduce calcium and magnesium ion concentration to 3 mg/l or below, and then 20 mg/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were added to the water. The pH of the water was in the range of 6.5 to 7.5.
______________________________________(Stabilizing bath) (unit: g)______________________________________Sodium p-toluenesulfinate 0.03Polyoxyethylene p-monononylphenyl ether 0.2(average degree of polymerization: 10)Disodium ethylenediaminetetraacetate 0.051,2,4-Triazole 1.31,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine 0.75Water ad 1.0 lpH 8.5______________________________________TABLE 2 Color development time forProcess No. Color developing agent obtaining given magenta density______________________________________201 P-5 2 min 50 sec202 Comp. compound-1 3 min 40 sec203 Comp. compound-2 longer than 10 min204 Comp. compound-3 2 min 20 sec205 Comp. compound-4 1 min 50 sec206 Comp. compound-5 2 min 30 sec207 D-2 2 min 20 sec208 D-10 2 min 00 sec209 D-11 1 min 30 sec210 D-12 1 min 50 sec______________________________________ Difference Difference in Difference in in yellowProcess No. yellow density cyan density fog density Remarks______________________________________201 +0.03 -0.02 +0.02 Comp. Ex.202 -0.55 -0.22 +0.25 Comp. Ex.203 Comp. Ex.204 -0.88 -0.42 +0.49 Comp. Ex.205 -0.96 -0.57 +1.55 Comp. Ex.206 -0.58 -0.28 +0.24 Comp. Ex.207 +0.21 +0.07 +0.10 Invention208 +0.13 +0.06 +0.04 Invention209 -0.04 -0.05 -0.07 Invention210 +0.05 -0.12 +0.07 Invention______________________________________
It is apparent from Table 2 that with the color developing agent of the present invention or each of the comparative compounds 3 to 5, the magenta image density can be obtained in a development process time far shorter than that necessitated when P-5 (processing solution No. 201) is used.
It will be understood that although a high rapidness can be attained with the comparative compounds 3 to 5, it is not easy to obtain a sufficient yellow density or cyan density and yellow fog density is high when they are used.
With the color developing agent of the present invention, the yellow density and cyan density could be remarkably improved while the yellow fog density could be kept low.
Namely, by using the developing agent of the present invention, the rapidness of the process could be realized, yellow density and cyan density could be Secured while yellow fog density could be kept low.
Example 2
The same sample 101 as that used in Example 1 was exposed. After the development by using the compound (D-10) of the present invention as the color developing agent in the color developer by a method which will be described below, a desired gradation could be obtained in a color development time of as short as only 60 seconds. Another advantage was that the fog density was low. The similar results could be obtained when the compound (D-10) was replaced with compound (D-2), (D-11) or (D-12).
Development steps and compositions of processing liquids:
______________________________________Step Temp. Time______________________________________Color development 45.degree. C. 60 secBleach-fixing 45.degree. C. 60 secWashing with water (1) 40.degree. C. 15 secWashing with water (2) 40.degree. C. 15 secWashing with water (3) 40.degree. C. 15 secStabilization 40.degree. C. 15 secDrying 80.degree. C. 30 sec______________________________________
The washing with water was conducted with three tanks by counter-current method from (3) to (1).
(Washing water)
______________________________________Liquid composition:______________________________________(Color developer) Mother liquid (g)______________________________________Diethylenetriaminepentaacetic acid 4.01-Hydroxyethylidene-1,1-diphosphonic acid 3.0Sodium sulfite 4.0Potassium carbonate 50.0Potassium bromide 4.0Potassium iodide 1.3 mgHydroxylamine sulfate 4.0Color developing agent (D-10) 19.2Water ad 1.0 lpH (adjusted with potassium hydroxide and 10.05sulfuric acid)______________________________________(Bleach-fixing bath) (unit: mol)______________________________________Chelating agent represented by formula A 0.17Ferric nitrate nonahydrate 0.15Ammonium thiosulfate 1.25Ammonium sulfite 0.10M-carboxybenzenesulfinic acid 0.05Water ad 1.0 lpH (adjusted with acetic acid and ammonia) 5.8______________________________________
Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B; a product of Rohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400; a product of Rohm & Haas Co.) to reduce calcium and magnesium ion concentration to 3 mg/l or below, and then 20 mg/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were added to the water. The pH of the water was in the range of 6.5 to 7.5.
______________________________________(Stabilizing bath) Mother liquid (g)______________________________________1,2-Benzoisothiazoline-3-on 0.1Polyoxyethylene p-monononylphenyl ether 0.2(average degree of polymerization: 10)Water ad 1.0 lpH (adjusted with ammonia water and 8.50hydrochloric acid)______________________________________ ##STR9##
Example 3
The same sample 101 as that used in Example 1 was exposed and then processed with the color developing agent D22 or D41 in the color developer by process Nos. 201 to 210. The image fastness of the samples o a magenta density of 2.0 were examined to find that an excellent image fastness was obtained with the compounds of the present invention.
Example 4
A sample 301 in Example 3 of J. P. KOKAI No. Hei 5-188550 was exposed and then developed by the same method as that described in that specification except that the color developing agent in the color developer was replace with an equimolar amount of the color developing agent (D2), (D10), (D11) or (D12). The development time could be reduced, the fog density was low, and the difference among the magenta density, yellow density and cyan density was only slight favorably.
When the color developing agent of the present invention suitable for the rapid process is used, an image having sufficient yellow, magenta and cya image densities, a low fog density and high image fastness can be obtained.

Number	Name	Date	Kind
2304953	Peterson	Dec 1942
5310634	Mikoshiba et al.	May 1994

Number	Date	Country
53-69035	Jun 1978	JPX
4-45440	Feb 1992	JPX
5-113635	May 1993	JPX

Color developing agent, processing composition and color image-forming method

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