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Matched Legal Cases: ['Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 60', 'Application No. 60', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 59', 'Application No. 60']

Patent US4983494 - Image forming process including heating step - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsAn image is formed in a photographic element by a process comprising a step of heating a heat-developable photosensitive material in the presence of a specific compound which typically releases a phenylmercaptotetrazole having a substituted benzene ring and serving as a development retarder....http://www.google.com/patents/US4983494?utm_source=gb-gplus-sharePatent US4983494 - Image forming process including heating stepAdvanced Patent SearchPublication numberUS4983494 APublication typeGrantApplication numberUS 07/423,674Publication dateJan 8, 1991Filing dateOct 18, 1989Priority dateOct 16, 1985Fee statusPaidPublication number07423674, 423674, US 4983494 A, US 4983494A, US-A-4983494, US4983494 A, US4983494AInventorsHiroshi Kitaguchi, Masatoshi KatoOriginal AssigneeFuji Photo Film Co., Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (8), Referenced by (23), Classifications (15), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetImage forming process including heating step
US 4983494 AAbstract
An image is formed in a photographic element by a process comprising a step of heating a heat-developable photosensitive material in the presence of a specific compound which typically releases a phenylmercaptotetrazole having a substituted benzene ring and serving as a development retarder.
1. A process for forming an image comprising a step of heating a heat-developable photosensitive material containing a silver halide in the presence of a compound selected from the group consisting of compounds of general formula (I-II): ##STR51## wherein Z represents a group of nonmetallic atoms necessary to complete a phenyltetrazole ring in which the phenyl radical has attached thereto a substituent selected from the group consisting of: ##STR52## wherein R' is a substituted or unsubstituted alkyl radical having 3 to 20 carbon atoms or a substituted or unsubstituted aryl radical, and R" is a hydrogen atom or a radical as defined for R',L1 is a valence bond or a substituted or unsubstituted divalent radical, p and q each are an integer of 1 or 2, and n is an integer of 0 or 1;compounds of general formula (II--II): ##STR53## wherein Z represents a group of nonmetallic atoms necessary to complete a phenyltetrazole ring in which the phenyl radical has attached thereto a substituent selected from the group consisting of: ##STR54## wherein R' is a substituted or unsubstituted alkyl radical having 3 to 20 carbon atoms or a substituted or unsubstituted aryl radical, and R" is a hydrogen atom or a radical as defined for R', R1 and R2 may be the same or different and are individually selected from a hydrogen atom and an alkyl radical having 1 to 4 carbon atoms, s and t each are an integer of 0 to 3 and may be the same or different, X1 and X2 may be the same or different and individually selected from an ester linkage, a substituted or unsubstituted amide linkage, and an ether linkage, L2 is selected from an alkylene, phenylene, and xylylene radical, when X1 and X2 are amide linkages, the substituents on the nitrogen may be bonded to form a heterocyclic ring together with parts of L2, X1, and X2, and m and r each are an integer of 0 or 1; and compounds of general formula (III-I): ##STR55## wherein u is an integer of 1 or 2, R5 represents a substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or phenyul radical when u is 1, and R5 represents a substituted or unsubstituted phenylene or alkylene radical when u is 2, R6 represents a substituted or unsubstituted alkyl having at least 3 carbon atoms or a cycloalky1 radical, and --(L)13 represents a valence bond or ##STR56## wherein R7 is selected from a hydrogen atom and the radicals defined for R6 and may be the same as or different from R6. 2. The image forming process of claim 1 wherein the heat-developable photosensitive material further comprises a dye-providing substance which produces or releases a mobile dye in proportion or counter-proportion to the reducing reaction of the silver halide to silver.
3. The image forming process of claim 1 wherein said compound is of the general formula (I-II).
4. The image forming process of claim 1, wherein said compound is of the general formula (II--II).
5. The image forming process of claim 1, wherein said compound is of the general formula (III-I).
This is a continuation of application Ser. No. 281,866, filed Dec. 6, 1988 now abandoned which is a continuation of application Ser. No. 981,970 filed Oct. 15, 1986 now abandoned.
This invention relates to an image forming process including a heating step, and more particularly, to a process for forming images by heating using a precursor of a development retarder.
Heat developable photosensitive materials and their image forming processes are well known in the art and described in the literature, inter alia, "Fundamentals of Photographic Engineering", Corona Publishing K.K., Tokyo, Japan (1979), pages 553-555; "Image Information", April 1978, page 40; and Nebletts Handbook of Photography and Reprography, 7th ed., Van Nostrand Reinhold Company, pages 32-33.
A number of methods have been proposed for producing color images through heat development, for example,
a process for forming color images using a coupler as a dye-providing substance (see U.S. Pat. Nos. 3,531,286; 3,761,270; and 4,021,240; Belgian Patent No. 802,519; and Research Disclosure, September 1975, pages 31-32),
a process of forming images using a dye having a nitrogen-containing heterocyclic group incorporated in its dye moiety as a dye-providing substance (see Research Disclosure, May 1978, pages 54-58, RD-16966),
a process based on silver dye bleaching (see Research Disclosure, April 1976, pages 30-32-, RD-14433; ibid, December 1976, pages 14-15, RD-15227; and U.S. Pat. No. 4,235,957), and
a process for forming a color image using a leuco dye (see U.S. Pat. Nos. 3,985,565 and 4,022,617).
These color image forming processes, however, have their own drawbacks and commonly suffer from the insufficient shelf storage of photosensitive material that the material deteriorates with a lapse of time as exemplified by increasing fog. Proposed as a solution of this problem is the use of a reducing dye-providing substance capable of releasing a hydrophilic dye as disclosed in Japanese Patent Application Kokai No. 58-58543. This proposal has succeeded in significantly overcoming the technical problems of the prior art processes.
Nevertheless, because of the absence of development inhibiting or retarding means, the aforementioned image forming processes based on heat development cannot avoid such problems as increasing fog due to overdevelopment and varying photographic performance due to varying heating temperature, and thus they are still difficult to always produce consistent images.
On the other hand, several development inhibiting techniques are known in the conventional diffusion transfer photography. For example, development inhibitor precursors and color diffusion transfer photographic materials using same are described in Japanese Patent Publication Nos. 60-19498 and 60-29709. These patents describe or suggest nowhere the application to heat developable photosensitive material. Quite unsatisfactory results could be obtained when the compounds disclosed in these patents are added to heat developable photosensitive material.
An object of the present invention is to provide a novel and improved image forming process including a heat step wherein the development process terminates at the point of optimum development, avoiding fogging due to overdevelopment and providing consistent photographic performance regardless of varying heating temperature.
According to the present invention, there is provided a process for forming an image comprising a step of heating in the presence of a compound having the general formula:
R--(SO2 --CH2 CH2 --S--A)n             (I)
wherein n is an integer having a value of 1 or 2,
R represents a monovalent radical selected from the group consisting of a substituted or unsubstituted alkyl, cycloalkyl, aralkyl, and aryl radical when n is 1, and R represents a divalent linking radical when n is 2, and
A represents a radical selected from the group consisting of a substituted or unsubstituted phenyl and nitrogen-containing heterocyclic radical, and two A's may be the same or different when n is 2.
More specifically, the divalent linking radical represented by R when n is 2 is selected from the group consisting of a phenylene radical, an alkylene radical, a radical having the formula: ##STR1## wherein L represents a bond or a substituted or unsubstituted divalent radical, p and q each are an integer of 1 or 2, and m is an integer of 0 or 1, and a radical having the formula: ##STR2## wherein R1 and R2 are independently selected from a hydrogen atom and an alkyl radical having 1 to 4 carbon atoms,
X1 and X2 are independently selected from an ester linkage, a substituted or unsubstituted amide linkage, and an ether linkage,
u and t each are an integer of 0 to 3, and
r and s each are an integer of 0 or 1.
In a first preferred embodiment of the present invention, the image forming process include heating in the presence of a compound having the general formula (I--I): ##STR3## wherein A and A' may be the same or different and are individually selected from substituted or unsubstituted phenyl radicals and 5- or 6-membered nitrogen-containing heterocyclic radicals; L represents a single bond or a substituted or unsubstituted divalent radical; p and q each are an integer of 1 or 2; and n is an integer of 0 or 1.
The substituents on the phenyl radicals represented by A and A' in formula (I--I) include alkyl radicals (preferably, having 1 to 4 carbon atoms, for example, methyl and ethyl), alkoxy radicals (preferably, having 1 to 4 carbon atoms, for example, methoxy and ethoxy), nitro radical, halogen atoms (such as chloro), alkoxycarbonyl radicals (preferably the alkyl moiety having 1 to 4 carbon atoms, for example, methoxycarbonyl and ethoxycarbonyl), substituted or unsubstituted carbamoyl radicals (preferred substituents being alkyl radicals having 1 to 4 carbon atoms and phenyl radical), and substituted or unsubstituted sulfamoyl radicals (preferred substituents being alkyl radicals having 1 to 4 carbon atoms and phenyl radical).
The hetero ring of the nitrogen-containing heterocyclic radicals represented by A and A' in formula (I-I) may be fused to a benzene ring or replaced with commonly used substituents such as phenyl radical. Examples of the nitrogen-containing heterocyclic radicals include tetrazole rings such as tetrazole ring and phenyltetrazole ring; triazole rings such as benzotriazole ring and 1,2,4-triazole ring; diazole rings such as benzimidazole ring and imidazole ring; pyrimidine rings such as pyrimidine ring; monoazole rings such as benzothiazole ring and benzooxazole ring, and the like. Preferred are nitrogen-containing heterocyclic radicals having at least two heteroatoms such as tetrazole rings and diazole rings. Most preferred are phenyltetrazole ring and benzimidazole ring. Preferably, A and A' are the same.
The divalent radical represented by L in formula (I-I) is preferably selected from alkylene radicals having 1 to 10 carbon atoms, arylene radicals having 6 to 10 carbon atoms, divalent radicals of ##STR4## and a combination of two or more of these divalent radicals; wherein R represents a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms (for example, methyl, ethyl, n-propyl, and n-butyl radicals), aryl radical having 6 to 10 carbon atoms (for example, phenyl radical), or an aralkyl radical having 7 to 10 carbon atoms (for example, benzyl radical). When L is not a single bond, these divalent radicals may be further substituted with a substituent such as alkyl and aryl radicals.
More particularly, preferred among the compounds of formula (I-I) are compounds having the general formula (I-II): ##STR5##
In formula (I-II), Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic radical. The preferred nitrogen-containing heterocyclic radicals are tetrazole rings, and most preferably 1-phenyltetrazole rings.
The phenyl radical of the 1-phenyltetrazole ring may have a suitable substituent. The preferred substituents include ##STR6## wherein R is typically a substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl radical and R is typically a hydrogen atom or a radical as defined for R. Particularly preferred substituents are --OR and --NHCOR. In these substituents, R1 is preferably a substituted or unsubstituted alkyl or substituted or unsubstituted aryl radical, and most preferably a straight chain or branched alkyl having up to 30 carbon atoms, especially 3 to 20 carbon atoms.
In general formula (I-II), L2, p, q, and n are as defined in formula (I-I). Preferably, p and q are equal to 1 and n is equal to 0. Preferably, L1 is selected from alkylene radicals having 1 to 6 carbon atoms (for example, methylene, ethylene, trimethylene, and hexamethylene radicals), phenylene and xylylene radicals and these radicals combined with an ether linkage.
It is contemplated in the present invention that the compound of formula (I-I) releases a development retarder: A-SH(A'-SH) according to the following reaction scheme when heated. ##STR7## This reaction proceeds by itself during heat development, but is accelerated with a supply of a base. It is thus very advantageous to combine the compound of the present invention with a base or base precursor.
The compounds of formula (I-I) are characterized by the presence of at least one hydroxyl radical. The presence of hydroxyl radical contributes to an improved development inhibiting effect particularly when p=q=1. The development retarder precursors having a hydroxyl substituent are disclosed nowhere in the afore-mentioned Japanese Patent Publication Nos. 60-19498 and 60-29709. Such a development inhibiting effect in heat developable photosensitive material are quite unexpected.
Some preferred, non-limiting examples of the compounds of general formula (I-I) are given below. ##STR8## Compound No. 109 Compound No. 108 wherein --R=--n--C4 H9 Compound No. 110
Compound No. 108 wherein --R=--n--C6 H13 Compound No. 111
Compound No. 108 wherein --R=--n--C8 H17 Compound No. 112
Compound No. 108 wherein --R=--n--C10 H21 Compound No. 113
Compound No. 108 wherein --R=--n--C12 H25 Compound No. 114
Compound No. 108 wherein --R=--n--C14 H29 Compound No. 115
Compound No. 108 wherein --R=--n--C16 H33 Compound No. 116
Compound No. 108 wherein --R=--CH2 CH2 OCH3 ##STR9##
These compounds are generally synthesized by adding a thiol of formula (I-IV) to a compound having two vinylsulfonyl radical per molecule and represented by formula (I-III). ##STR10##
A--SH                                                      (I-IV)
In formulae (I-III) and (I-IV), A, L, p, q, and n are as defined for formula (I-I). The compounds having two vinylsulfonyl radical per molecule as represented by formula (I-III) are well known in the photographic art as a hardener for gelatin binder and their preparation is detailed, for example, in Japanese Patent Publication No. 50-358067; Japanese Patent Application Kokai Nos. 53-41221, 54-30002, 53-57257; and U.S. Patent No. 3,642,486. Inter alia, Japanese Patent Application Kokai No. 53-57257 describes the synthesis of a compound having a hydroxy radical as represented by formula (I-III).
Some examples of synthesis of the present compounds by addition reaction of thiol of formula (I-IV) to compound of formula (I-III) are presented below.
Synthesis of compound No. 101
To 1,3-bis(vinylsulfonyl)-2-propanol (24 grams) were added 1-phenyl-5-mercaptotetrazole (36 grams), sodium acetate (15 grams) and acetic acid (200 ml). The mixture was stirred at 60� C. for 3 hours. The reaction solution was poured into methanol (1 liter) whereupon crystals precipitated. The crystal precipitate was filtered off and recrystallized from acetone (1 liter), yielding compound No. 101. Yield 30 grams, m.p. 144� C. The structure of the compound was identified by NMR and IR spectra.
Synthesis of compound No. 119
The procedure of Synthesis 1 was repeated except that the 1-phenyl-5-mercaptotetrazole was replaced by 1-(m-butyrylaminophenyl)-5-mercaptotetrazole (53.2 grams). There was obtained Compound No. 119 in a yield of 263.2 grams. m.p. 153�-155� C.
Synthesis of compound No. 125
To 1,3-bis(vinylsulfonyl)-2-propanol (43.2 grams) were added 1-(m-ethylhexanoylaminophenyl)-5-mercaptotetrazole (120 grams), sodium acetate (30 grams) and acetic acid (400 ml). The mixture was stirred at 60� C. for 21/2 hours. The reaction solution was poured into water (1.5 liters) whereupon crystals precipitated. The precipitate was extracted with ethyl acetate. The ethyl acetate layer was washed with water and salt water, and dried with sodium sulfate, and the solvent distilled off under vacuum. Methanol (600 ml) was added to the residue and the solution cooled. The resulting crystal precipitate was filtered off, yielding compound No. 125. Yield 114.5 grams, m.p. 155�-157� C.
Synthesis of compound No. 122
To 1,3-bis(vinylsulfonyl)-2-propanol (18 grams) were added 1-(n-caproylaminophenyl)-5-mercaptotetrazole (44.5 grams), sodium acetate (12.3 grams), acetic acid (175 ml), and N,N-dimethylformamide (25 ml). The mixture was stirred at 75�-78� C. for 4 hours. Methanol (250 ml) and water (25 ml) were added to the reaction solution, which was cooled to 8� C. The resulting crystal precipitate was filtered off and recrystallized from a solvent mixture of ethanol (350 ml), N,N-dimethylformamide (50 ml), and water (35 ml), yielding compound No. 122. Yield 50.5 grams, m.p. 167� C.
Synthesis of compound No. 127
To 1,3-bis(vinylsulfonyl)-2-propanol (7.93 grams) were added 1-(n-lauroylaminophenyl)-5-mercaptotetrazole (25.1 grams), sodium acetate (5.5 grams), acetic acid (150 ml), and DMF (17 ml). The mixture was stirred at 75�-78� C. for 5 hours and crystals precipitated during stirring. Methanol (150 ml) was added to the reaction solution, which was cooled to 5� C. The resulting crystal precipitate was filtered off (30.3 grams). It was recrystallized from a solvent mixture of acetone (150 ml) and DMF (38 ml), yielding compound No. 127. Yield 25.3 grams, m.p. 164�-166� C.
Synthesis of compound No. 129
The procedure of Synthesis 5 was repeated except that the 1-(n-lauroylaminophenyl)-50mercaptotetrazole was replaced by 1-(n-palmitoylaminophenyl)-5-mercaptotetrazole (28.8 grams). There was obtained Compound No. 129 in a yield of 28.6 grams. m.p. 171�-172� C.
In a second preferred embodiment of the present invention, the image forming process include heating in the presence of a compound having the general formula (II-I): ##STR11## wherein A and A' may be the same or different and are individually selected from a substituted or unsubstituted phenyl radical and a 5- or 6-membered nitrogen-containing heterocyclic radical;
R1 and R2 may be the same or different and are individually selected from a hydrogen atom and an alkyl radical having 1 to 4 carbon atoms;
p and q each are an integer of 0 to 3 and may be the same or different;
X1 and X2 may be the same or different and individually selected from an ester linkage, a substituted or unsubstituted amide linkage including a sulfonamide linkage, and an either linkage;
L is selected from an alkylene, phenylene, and xylylene radical;
when X1 and X2 are amide linkages, the substituents on the nitrogen may be bonded to form a heterocyclic ring together with parts of L, X1, and X2, and
n and m each are an integer of 0 or 1.
The substituents on the phenyl radicals represented by A and A' in formula (II-I) include alkyl radicals (preferably, having 1 to 4 carbon atoms, for example, methyl and ethyl), alkoxy radicals (preferably, having 1 to 4 carbon atoms, for example, methoxy and ethoxy), nitro radical, halogen atoms (such as chloro), alkoxycarbonyl radicals (preferably the alkyl moiety having 1 to 4 carbon atoms, for example, methoxycarbonyl and ethoxycarbonyl), substituted or unsubstituted carbamoyl radicals (preferred substituents being alkyl radicals having 1 to 4 carbon atoms and phenyl radical), and substituted or unsubstituted sulfamoyl radicals (preferred substituents being alkyl radicals having 1 to 4 carbon atoms and phenyl radical).
The hetero ring of the nitrogen-containing heterocyclic radicals represented by A and A' in the formula (II-I) may be fused to a benzene ring or replaced with commonly used substituents such as phenyl radical. Examples of the nitrogen-containing heterocyclic radicals include tetrazole rings such as tetrazole ring and phenyltetrazole ring; triazole rings such as benzotriazole ring and 1,2,4-triazole ring; diazole rings such as benzimidazole ring and imidazole ring; pyrimidine rings such as pyrimidine ring; monoazole rings such as benzothiazole ring and benzooxazole ring, and the like. Preferred are nitrogen-containing heterocyclic radicals having at least two heteroatoms such as tetrazole rings and diazole rings. Most preferred are phenyltetrazole ring and benzimidazole ring. Preferably, A and A' are the same.
The alkyl radicals represented by R1 and R2 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, and tert-butyl radicals.
When X1 and X2 are amide linkages, they may have a substituent attached to the nitrogen, for example, an alkyl and aryl radical. The heterocyclic ring which L forms together with parts of X1 and X2 may be substituted or unsubsituted. Examples of the heterocyclic ring include perhydrotriazine ring, imidazoline ring, piperadine ring and perhydropyrimidine ring. Particularly among them, the perhydrotriazine ring may be substituted, typically with a substituent of the formula: ##STR12## wherein A, R1 and p are as defined above.
More particularly, preferred among the compounds of formula (II-I) are compounds having the general formula (II-II): ##STR13##
In formula (II-II), Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic radical. The preferred nitrogen-containing heterocyclic radicals are tetrazole rings and diazole rings, and most preferably 1-phenyltetrazole ring and benzimidazole ring.
The phenyl radical of the 1-phenyltetrazole ring may have a suitable substituent. The preferred substituents include ##STR14## wherein R is typically a substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl radical and R is typically a hydrogen atom or a radical as defined for R. Particularly preferred substituents are --OR and --NHCOR. In these substituents, R is preferably a substituted or unsubstituted alkyl or substituted or unsubstituted aryl radical, and most preferably a straight chain or branched alkyl having up to 30 carbon atoms, especially 3 to 20 carbon atoms.
In general formula (II-II), R, R, X1, X2, L and m, are as defined in formula (II-I) and r has the same meaning as n is has the same meaning as p and t has the same meaning as q. Preferably, s and t are equal to 0 or 1 and R and R are hydrogen atoms or methyl radicals. Preferably, L is selected from an alkylene radical having 1 to 6 carbon atoms (for example, methylene, ethylene, trimethylene, and hexamethylene radicals), phenylene, and xylylene radical.
Preferably, X1 and X2 are selected from an amide and ether linkage. Preferably both n and m are equal to 1, when both X1 and X2 are amide linkages.
Particularly preferred are compounds of the following general formula (II-III): ##STR15## wherein Z, R1, R2, L, p, and q are as defined for formula (II-II), R3 and R4 are individually selected from a hydrogen atom, alkyl radical having 1 to 4 carbon atoms (for example, methyl, ethyl, isopropyl, and butyl radicals), and phenyl radical. R3 and R4 may be mutually combined to form a heterocyclic ring together with L and the two adjacent nitrogen atoms.
More preferred examples included within the scope of the above formula are compounds of the following general formula (II-IV). Preferred examples of these compounds wherein the heterocyclic ring is further substituted are also given below by the general formula (II-V). ##STR16##
In formulae (II-IV) and (II-V), Z, R1, R2, p, and q are as defined for formula (II-II), r is equal to 0 or 1, and R5 represents hydrogen atom or methyl.
When X1 represents an ether linkage, desirably both n and m are equal to 0. Particularly preferred are those compounds of the general formula (II-VI): ##STR17## wherein Z, p, and q are as defined for formula (II-II).
Preferably p=q in the foregoing formulae (II-I to IV) and (II-VI), and p=q=r in the foregoing formula (II-V).
It is contemplated in the present invention that the compound of formula (II-I) releases a development retarder: A-SH(A'-SH) according to the following reaction scheme when heated. ##STR18## This reaction proceeds by itself during heat development, but is accelerated with a supply of a base. It is thus very advantageous to combine the compound of the present invention with a base or base precursor.
The compounds of formula (II-I) are disclosed in Japanese Patent Application Kokai No. 59-105640 as being solely used in color diffusion transfer photography. The laid-open specification contains no suggestion about the possible application of these compounds to heat-developable photosensitive material. Also lacking is the description or teaching that the compounds release mercaptoazoles which are compounds having a long chain acylamino or long chain alkoxy radical.
Because of mercaptoazole release, the compounds of formula (II-I) are advantageous particularly when a process of generating a base by mixing a difficultly soluble metal compound with a compound capable of complexing with the metal ion of the difficultly soluble metal compound (as will be described later) is applied to a photosensitive material containing the present compound.
Some preferred, no-limiting examples of the compounds of general formula (II-I) are given below. ##STR19##
These compounds can be synthesized by the method described in the aforementioned Japanese Patent Application Kokai No. 59-105640. Some examples of sythesis of these compounds are presented below.
Synthesis of compound No. 203
To 1,3-bis(vinylsulfonylacetamide)propane (6.1 grams) were added 1-phenyl-5-mercaptotetrazole (7.1 grams), sodium acetate (3.2 grams) and acetic acid (30 ml). The mixture was stirred at 60� C. for 2 hours. Ethyl acetate (63 ml) and water (27 ml) were added to the reaction solution, which was cooled with ice. The resulting crystal precipitate was filtered off and recrystallized from acetone (45 ml), yielding compound No. 203. Yield.7.6 grams, 61% of the theory, m.p. 75�-78� C.
Synthesis of compound No. 220
The procedure of Synthesis 21 was repeated except that the 1-phenyl-5-mercaptotetrazole was replaced by 1-(p-methoxyethoxyphenyl)-5-mercaptotetrazole (9.16 grams). There was obtained compound No. 220 in a yield of 10.84 grams. Yield 74%, m.p. 85�-88� C.
Synthesis of compound No. 225
To 1,3-bis(vinylsulfonylacetamide)propane (10.15 grams) were added 1-(m-lauroylaminophenyl)-5-mercaptotetrazole (23.6 grams), sodium acetate (5 grams) and acetic acid (100 ml). The mixture was stirred at 75� C. for 5 hours. Methanol (100 ml) was added to the reaction solution, which was cooled. The resulting crystal precipitate was filtered off and recrystallized from a solvent mixture of acetone (250 ml), methanol (200 ml), and DMF (40 ml), yielding compound No. 225. Yield 26.1 grams, 80% of the theory, m.p. 138�-139� C.
Synthesis of compound No. 227
The procedure of Synthesis 23 was repeated except that the 1-(m-lauroylaminophenyl)-5-mercaptotetrazole was replaced by 1-(m-palmitoylaminophenyl)-5-mercaptotetrazole (26.8 grams). The resulting crude crystals were recrystallized from a solvent mixture of acetone (300 ml), methanol (100 ml), and DMF (130 ml), yielding compound No. 227. Yield 29.6 grams, 82% of the theory, m.p. 167�-168� C.
In a third preferred embodiment of the present invention, the image forming process include heating in the presence of a compound having the general formula (III-I): ##STR20##
wherein u is an integer of 1 or 2,
R5 represents a substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl radical when u is 1, and R5 represents a substituted or unsubstituted phenylene or alkylene radical when u is 2,
R6 represents a substituted or unsubstituted alkyl having at least 3 carbon atoms, cycloalkyl, aralkyl, or aryl radical, and --(L)-- represents a single bond or ##STR21## wherein R7 is selected from a hydrogen atom and the radicals defined for R6 and may be the same as or different from R6.
When u is equal to 1, the alkyl radicals represented by R5 include straight chain or branched alkyl radicals having 1 to 18 carbon atoms, for example, ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-decyl, and n-dodecyl. These alky radicals may be substituted with such a substituent as halo, alkoxy, cyano, and substituted or unsubstituted carbamoyl radicals.
The cycloalkyl radicals represented by R5 include 5-or 6-membered cycloalkyl radicals having 5 to 10 carbon atoms. Typical examples are cyclopentyl and cyclohexyl radicals. The aralkyl radicals represented by R5 include benzyl and β-phenetyl radicals.
The aryl radicals represented by R5 are preferably aryl radicals having 6 to 18 carbon atoms, for example, phenyl, naphthyl, and anthryl radicals. The aryl radicals may be substituted with such a substituent as substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, halo, alkyl- or aryl-disubstituted amino, acyl amino, sulfonyl amino, cyano, nitro, alkyl or aryl sulfonyl, oxycarbonyl, carbonyloxy, substituted or unsubstituted carbamoyl, and substituted or unsubstituted sulfamoyl radicals.
When u is equal to 2, the phenylene radical represented by R5 may vary in para-, meta-, and ortho-forms and be substituted with the same substituents as defined for the phenyl radicals represented by R5 when u=1.
The alkylene radicals represented by R5 include methylene, ethylene, propylene, and butylene radicals. They may be substituted with the same substituents as defined for the alkyl radicals represented by R5 when u=1.
Preferably, u is equal to 1 and R5 is a substituted or unsubstituted alkyl or aryl radical. More preferably R5 are substituted or unsubstituted aryl radicals, and most preferably phenyl radicals having at least one electron attractive group (for example, nitro, halo, alkyl or aryl sulfonyl, substituted or unsubstituted carbamoyl or sulfamoyl, cyano, and oxycarbonyl group).
The alkyl radicals represented by R6 include straight chain or branched alkyl radicals having at least 3 carbon atoms, preferably 3 to 30 carbon atoms, and most preferably 5 to 20 carbon atoms. Typical examples are n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 1-ethylpentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pendadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, 1-heptyloctyl, and 2-heptylnonyl radicals.
The cycloalkyl radicals represented by R6 include cyclopentyl and cyclohexyl radicals.
The aralkyl radicals represented by R6 include benzyl and phenetyl radicals.
The aryl radicals represented by R6 are, for example, phenyl, naphthyl, and anthryl radicals. The aryl radicals may be substituted with such a substituent as defined for R5.
Preferably, R6 is a substituted or unsubstituted alkyl or aryl radical, and most preferably a straight chain alkyl radical.
Preferred among the radicals represented by --(L)-- are --O--, --NHCO--, --NHSO2 --. More particularly, --O-- may be attached at the para position, and --NHCO-- and --NHSO2 -- may be attached at the meta position position with respect to the nitrogen atom of the tetrazole ring.
The preferred compounds of general formula (III-I) are those represented by the following formula: ##STR22## wherein W is an electron attractive group and R2 is a straight chain alkyl.
It is contemplated in the present invention that the compound of formula (III-I) releases a development retarder of formula (III-IV) according to the following reaction scheme when heated. ##STR23## This reaction proceeds by itself during heat development, but is accelerated with a supply of a base. It is thus very advantageous to combine the compound of the present invention with a base or base precursor.
The compounds of formula (III-I) are characterized in that the released development retarder of formula (III-IV) has --(L)--R6. Analoguous compounds are disclosed in the afore-mentioned Japanese Patent Publication Nos. 60-19498 and 60-29709. In all the compounds described therein, the benzene ring attached to the tetrazole ring at its 1-position is unsubstituted. These patent publications refer nowhere to heat-developable photosensitive material. Furthermore, as will be illustrated in Examples, the application of the compounds described in these patent publications to a system as used in the present invention is little effective. The present invention becomes effective only when the compounds having --(L)--R2 are defined by the general formula are applied to heat-developable photosensitive material This is quite unexpected from the prior art knowledge.
Some preferred, non-limiting examples of the compounds of general formula (III-I) are given below. ##STR24##
The compounds of formula (III-I) are generally synthesized by Micheal addition reaction of a thiol compound of formula (III-IV) to a vinyl sulfone derivative of formula (III-III) according to the following scheme: ##STR25##
Some examples of synthesis of the present compounds are present below.
Synthesis of compound No. 306
A solution of p-chlorophenylvinylsulfonyl (10.1 grams), 1-(m-butyroylaminophenyl)-5-mercaptotetrazole (14 grams), and sodium acetate (4.5 grams) in acetic acid (60 ml) was stirred at 60� C. for 3 hours. The reaction solution was poured into water (200 ml) whereupon crystals precipitated. The resulting crude crystals were filtered off and recrystallized from a solvent mixture of 2/1 ethanol/acetone, yielding compound No. 306. Yield 18.7 grams, 80%, m.p. 167�-170� C.
Synthesis of compound No. 311
The procedure of Synthesis 31 was repeated except that the 1-(m-butyroylaminophenyl)-5-mercaptotetrazole was replaced by 1-[m-(2-ethylhexanoylaminophenyl)]-5-mercaptotetrazole (16.25 grams). The resulting crude crystals were recrystallized from a solvent mixture of 5/1 methanol/ethanol, yielding compound No. 311. Yield 15.9 grams, 61%, m.p. 157�-159� C.
Synthesis of compound No. 321
The procedure of Synthesis 31 was repeated except that the 1-(m-butyroylaminophenyl)-5-mercaptotetrazole was replaced by 1-[p-(2-methoxyethoxyphenyl)]-5-mercaptotetrazole (13.4 grams). The resulting crude crystals were recrystallized from ethanol, yielding compound No. 321. Yield 16.1 grams, 71%, m.p. 85�-86� C.
The amount of the compound of the present invention used varies with a particular compound and a system to which it is used, although it is generally up to 50% by weight of the total weight of a coating film containing the compound, preferably up to 30% by weight.
The compound of the present invention may be incorporated into a binder as a solution in a water-missible organic solvent or a solvent mixture of such organic solvent and water, examples of the organic solvent including methanol, ethanol, acetone, and dimethylformamide.
The hydrophobic compound of the present invention may be incorporated into a binder by an oil protect technique.
The hydrophobic compound of the present invention may be incorporated into a binder as finely divided particles by the method described in Japanese Patent Application Kokai No. 59-174830. This specification discloses a method for dispersing a base precursor in a binder as finely divided particles, and this method is also useful in dispersing hydrophobic additives including not only the hydrophobic compounds of the present invention, but other hydrophobic (particularly, difficultly soluble in organic solvent) additives, for example, acid precursors and antifogging precursors in a hydrophilic binder to produce a stable dispersion.
This dispersion method is particularly useful in dispersing the compounds of the present invention partly because many of them are difficultly soluble in usual organic solvents and partly because the possible inclusion in a coating film in crystal form substantially improves aging stability as compared with the inclusion as a solution in which the compound is once dissolved.
The compounds of the present invention may be used alone or in admixture of two or more. They may also be combined with another development inhibitor or retarder or another development inhibiting technique. Such compatible development inhibitors and development inhibiting techniques are known, for example, a method based on pyrolysis of aldoxime ester as disclosed in Japanese Patent Application Nos. 58-216928 and 59-48305, a method based on Lossen rearrangement as disclosed in Japanese Patent Application No. 59-85834, and a method using a carboxylate ester as disclosed in Japanese Patent Application No. 59-85836.
The image forming process including a heating step as used herein means that a heating step is involved in any one of image forming steps irrespective of whether the heating is for development or for transfer. Imagewise heating is also contemplated herein.
The heat-developable photosensitive materials used in an image forming process wherein heating is conducted for the purpose of development include such materials using silver halide and materials using diazo compounds. The compounds of the present invention may be added to these photosensitive materials, or when an image-receiving layer is provided on another support, to any desired one of layers on the support. Alternatively, they may be supplied from the outside during heating.
Most preferred heat-developable photosensitive materials are those using silver halide as a photosensitive element.
The heating temperature ranges from about 50� C. to about 250� C., more preferably from about 60� C. to about 180� C.
Useful are silver halide emulsions as disclosed in, inter alia, U.S. Pat. No. 4,500,626, col. 50; Research Disclosure, June 1978, pages 9-10 (RD 17029); and Japanese Patent Application Nos. 59-228551, 60-225176, and 60-228267, which are all incorporated herein by reference.
The organic compounds which can be used in the preparation of the organic silver salt oxidizing agents include those compounds disclosed in Japanese Patent Application No. 59-228551, pages 37-39 and U.S. Pat. No. 4,500,626. Also useful are silver salts of carboxylic acids having an alkynyl radical such as silver phenylpropiolate as disclosed in Japanese Patent Application No. 60-113235 and silver acetylene as disclosed in Japanese Patent Application No. 60-90089. These organic silver salts may be used alone or in combination of two or more.
The silver halides used in the practice of the present invention may be spectrally sensitized with methine dyes and other dyes. The dyes useful for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
Illustrative examples are the sensitizing dyes disclosed in Japanese Patent Application Kokai Nos. 59-80550 and 60-140335 and Research Disclosure, June 1978, pages 12-13 (RD 17029); and the sensitizing dyes of heat-decoloring nature disclosed in Japanese Patent Application Kokai No. 60-111239 and Japanese Patent Application No. 60-72967.
These sensitizing dyes may be used individually or as a combination thereof. A combination of sensitizing dyes is frequently used for supersensitization.
______________________________________U.S. Pat. No.______________________________________2,933,390      3,635,721    3,635,7213,743,510      3,615,613    3,615,6413,617,295      3,635,721.______________________________________
These sensitizing dyes may be added to the emulsion during, before or after chemical ripening, or before or after nucleation of silver halide grains according to the teachings of U.S. Patent Nos. 4,183,756 and 4,225,666.
The amount of the sensitizing dye is generally from 10-8 to 10-2 mol per mol of the silver halide.
Typical of the dye-providing substances which can be used in the present invention are couplers capable of oxidative coupling reaction to form a dye. These couplers may be either four or two equivalent couplers. Also useful are two equivalent couplers having an anti-diffusion group as an eliminatable group and thus forming a diffusible dye through oxidative coupling reaction. Illustrative examples of the developing agents and couplers are described in detail in, for example, T. H. James, "The Theory of the Photographic Process", 4th Ed., pages 291-334 and 354-361, and the following laid-open specifications.
______________________________________Japanese Patent Application Kokai Nos______________________________________58-123533      58-149046    58-14904759-111148      59-124399    59-17483559-231539      59-231540    60-295060-2951        60-14242     60-2347460-66249.______________________________________
Another class of dye-providing substances includes compounds having the function of releasing or diffusing a diffusible dye imagewise. The compounds of this type may be represented by the following formula [L,I]:
(Dye-X)n --Y                                          [L I]:
wherein Dye represents a dye group, a temporarily wavelength shortened dye group or a dye precursor group; X represents a single bond or a connecting group; and Y represents a group which, in correspondence or counter-correspondence to photosensitive silver salt having a latent image distributed imagewise, produces a difference in diffusibility of the compound represented by (Dye-X)n -Y or releases Dye, the diffusibility of Dye released being different from that of the compound represented by (Dye-X)n -Y; and n represents an integer of 1 or 2, when n=2, the Dye-X's may be the same or different.
Exemplary of the dye-providing substances having general formula [L I] there may be given dye developing reagents in the form of a hydroquinone-type developing reagent having a dye moiety attached thereto as disclosed in U.S. Pat. Nos. 3,134,764; 3,362,819; 3,597,200; 3,544,545; and 3,482,972. In addition, substances which release a diffusible dye through intramolecular nucleophilic substitution reaction are disclosed in U.S. Pat. No. 3,980,479, and substances which releases a diffusible dye through intramolecular rewind reaction of an isooxazolone ring are disclosed in Japanese Patent Application Kokai No. 49-111628.
Another system is proposed wherein the dye-providing substance is previously modified into an oxidant form having no dye releasing ability so that the modified substance may coexist with a reducing agent or precursor thereof. After development, the reducing agent which remains non-oxidized acts on the modified substance to reduce it, thereby releasing the diffusible dye. Typical examples of the dye-providing substances usable in such a system are described in Japanese Patent Application Kokai Nos. 53-110827, 54-130927, 56-164342, and 53-35533. Dye-providing substances releasing a diffusible dye through a similar mechanism are disclosed in Japanese Patent Application No. 60-244873, which describes compounds which undergo cleavage of their N-O linkage under the action of the remaining reducing agent to release a diffusible dye.
Also useful are non-diffusible (LDA) compounds which undergo donor-acceptor reaction in the presence of a base to release a diffusible dye, but substantially stops the dye release after reaction with an oxidant of a reducing agent as disclosed in Japanese Patent Application Kokai No. 59-185333.
In the systems to which these substances are applied, a diffusible dye is released or diffused where no development has taken place and no dye is released or diffused where development has taken place.
Also known are substances which release a diffusible dye where development has occurred. Couplers having a diffusible dye as an eliminatable group and thus releasing a diffusible dye through reaction with an oxidant of a developing reagent, known as DDR couplers, are described in British Patent No. 1,330,524; Japanese Patent Publication No. 48-39165; U.S. Pat. No. 3,443,940 and the like.
The systems using these reducing agents have the serious problem that the resulting image can be contaminated with oxidation decomposition products of a reducing agent. To overcome this problem, dye-releasing (DRR) compounds have been proposed which themselves have a reducing ability without the need for a reducing agent. They may be advantageously used in the present invention. Typical examples of these compounds are dye-providing substances described in the following publications:
______________________________________U.S. Pat. Nos.         3,725,062,                           3,728,113,3,443,939,             3,928,312,                           4,053,312,4,055,428,             4,336,322,                           4,500,626.Japanese Patent Application Kokai Nos.59-65839,              59-69839,                           58-116537,57-179840,             53-3819, 51-104343Research Disclosure, RD 17465.______________________________________
Representative examples of these dye-providing substances are those compounds described in the above-incorporated U.S. Pat. No. 4,500,626, columns 22-44, most preferably the compounds identified therein as compounds (1)-(3), (10)-(13), (16)-(19), (28)-(30), (33)-(35), (38)(40), and (42)-(64).
The dye-providing substances employable other than the aforementioned include dye-silver compounds in which an organic silver salt is combined with a dye (see Research Disclosure, May 1978, pages 54-58), azo dyes useful in heat development silver dye bleaching process (see U.S. Pat. No. 4,235,957; Research Disclosure, April 1976, pages 30-32), and leuco dyes (see U.S. Pat. Nos. 3,985,565 and 4,022,617).
In the practice of the present invention, the dye-providing substances and other hydrophobic additives such as image formation accelerators as will be described later may be introduced into a layer of photosensitive element by any well-known methods, for example, the method described in U.S. Pat. No. 2,322,027. In this case, an organic solvent having a high boiling point as described in Japanese Patent Application Kokai Nos. 59-83154, 59-178451, 59-178452, 59-178453, 59-178454, 59-178455, and 59-178457 may be used, optionally in admixture with an organic solvent having a low boiling point in the range of from 50� C. to 160� C.
The amount of the high boiling organic solvent used in the present invention is up to 10 grams, preferably up to 5 grams per gram of the dye-providing substance.
In case the substance is substantially insoluble in water, it may be finely divided into particles before being incorporated in the binder although the aforementioned methods may also be applicable.
Moreover, various surface-active agents may be used when a hydrophobic substance like the dye-providing substance is dispersed in a hydrophilic colloid. For this purpose, the surface-active agents illustrated in Japanese Patent Application Kokai No. 59-157636, incorporated herein by reference, pages 37-38 may be used.
A reducing agent may desirably be used in the photosensitive element in the practice of the present invention. The reducing agents used herein include wellknown reducing agents and the above-mentioned dye-providing substances having reducing ability. Also included are reducing agent precursors which themselves have no reducing nature, but exhibit reducing nature under the action of a nucleophilic agent or heat during the development process.
Examples of the reducing agents used herein include those reducing agents described in U.S. Pat. No. 4,500,626, columns 49-50, U.S. Pat. No. 4,483,914, columns 30-31, Japanese Patent Application Kokai No. 60-140335, pages 17-18, and Japanese Patent Application Kokai Nos. 60-128438, 60128436, 60-128439, and 60-128437. Also useful are reducing agent precursors as disclosed in Japanese Patent Application Kokai Nos. 56-138736 and 57-40245, U.S. Pat. No. 4,330,617, and the like. Various combinations of reducing agents as described in U.S. Pat. No. 3,039,869 may also be used.
Further, in the present invention, it is possible to use a compound which activates development simultaneously with stabilizing the image. Particularly preferred compounds used herein are those described in U.S. Pat. No. 4,500,626.
The photosensitive element used in the practice of the present invention may contain a toning agent if desired. Useful toning agents are those described in Japanese Patent Application No. 59-268926, pages 92-93.
In order to provide a wide range of color within the chromaticity diagram using the three primary colors, yellow., magenta and cyan, the photosensitive elements used in the present invention should include at least three silver halide emulsion layers having sensitivity in different spectra. Combinations of three layers, typically blue-, green-, and red-sensitive layers, and green-, red-, and infraredsensitive layers are contemplated herein. Each of these photosensitive layers may be divided into two or more sublayers, if desired.
The photosensitive elements used in the practice of the present invention may further contain any of various additives well known for use in heat-developable photosensitive elements and possess in addition to the photosensitive layers, any layers including a protective layer, intermediate layer, antistatic layer, antihalation layer, release layer for facilitating separation from a dye-fixing element, and matte agent layer.
Exemplary of the additives there may be given plasticizers, matte agents, sharpness improving dyes, antihalation dyes, surface-active agents, brighteners, antisliding agents, antioxidants, anti-discoloration agents, etc. as described in Research Disclosure, June 1978, pages 9-15, and Japanese Patent Application No. 59-209563. More specifically, the protective layer or coat (PC) usually contains an organic or inorganic matte agent for adherence prevention. The protective layer may futher contain a mordant, a UV-absorber, etc. Each of the protective and intermediate layers may be comprised of two or more layers.
Particularly, systems of forming an image through diffusion transfer of a dye need the photosensitive and dye-fixing elements as requisite elements. They are generally classified into two typical forms, one form having photosensitive and dye-fixing layers separately applied on two separate supports and another form having both photosensitive and dye-fixing layers applied on a common support. With respect to the relation of the photosensitive element and the dye-fixing element to one another, to the support, and to a white reflective layer, reference may be made to the descriptions of Japanese Patent Application No. 59-268926, pages 58-59 and U.S. Pat. No. 4,500,626, col. 57.
The dye-fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. The mordants may be those well known in the photographic art, with illustrative examples being described in Japanese Patent Application No. 59-209563. The dye-fixing element may be provided with any auxiliary layers, for example, a protective layer, anti-curling layer, and release layer, if desired. The provision of a protective layer is particularly useful. One or more of these layers may contain a hydrophilic thermal solvent, plasticizer, anti-discoloration agent, UV-absorber, anti-sliding agent, matte agent, antioxidant, dispersed vinyl compound for increasing dimensional stability, surface-active agent, brightener, etc. In a system wherein heat development and dye transfer are simultaneously conducted in the presence of a minor amount of water, it is preferable from the standpoint of enhanced shelf stability of photosensitive element to contain a base and/or base precursor (as will be described later) in the dye-fixing element. Illustrative examples of these additives are described in Japanese Patent Application No. 59-209563, pages 101-120.
An image formation promotor may also be used in the photosensitive element and/or dye-fixing element in the practice of the present invention. The image formation promotors have the functions of promoting such reaction as redox reaction of a silver salt-oxidizing agent with a reducing agent, formation of a dye from a dye-providing substance, decomposition of a dye or release of a mobile dye, and promoting transfer of a dye from a photosensitive material layer to a dye-fixing layer. From their physical-chemistry, they may be classified into bases, base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surface-active agents, and compounds capable of interacting with silver or silver ion. It should be noted that these compounds generally have multiple functions and thus possess some of the abovementioned promoting effects combined. For further detail, reference is to be made to Japanese Patent Application No. 59-213978, pages 67-71.
A number of other base producing methods are known and any of the compounds used in these methods are useful as the base precursor. For example, Japanese Patent Application No. 60-169585 discloses a method for producing a base by mixing a difficultly soluble metal compound with a compound (complexing compound) capable of forming a complex with the metal ion of the metal compound, and Japanese Patent Application No. 60-74702 discloses electrolytic base generation.
The former method is particularly effective. Examples of the difficultly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, and barium. The complexing compounds are detailed in, for example, A. E. Martell and R. M. Smith, "Critical Stability Constants", Vol. 4 and 5, Plenum Press. Some illustrative examples of the complexing compounds include salts of aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (including mono-, di-, tri-, and tetracarboxylic acids with or without such a substituent as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino, etc.), hydroxamic acids, polyacrylic acids, and polyphosphoric acids with alkali metals, guanidines, amidines, and quaternary ammonium. It is advantageous to separately add the difficultly soluble metal compound and the complexing compound to the photosensitive element and the dye-fixing element, respectively, or vice verse.
A hydrophilic binder may be employed in the photosensitive element and/or dye-fixing element in the practice of the present invention. The typical hydrophilic binder is a transparent or translucent hydrophilic binder, examples of which include natural substances, for example, proteins such as gelatin, gelatin derivatives and cellulose derivatives and polysaccharides such as starch, gum arabic, etc.; and synthetic polymers, for example, water-soluble polyvinyl compounds such as polyvinyl pyrrolidone, acrylamide polymer, etc. Another example of the synthetic polymer compound is a dispersed vinyl compound in a latex form which is used for the purpose of increasing the dimensional stability of a photographic material. These binders may be used alone or in admixture.
The binders may be coated in amounts of up to 20 grams per square meter, preferably up to 10 grams per square meter, and most preferably up to 7 grams per square meter.
Any of the layers of the heat-developable photosensitive element and the dye-fixing element according to the present invention, including photographic emulsion, dye-fixing and other layers, may contain inorganic or organic hardeners Illustrative examples of the hardeners are those set forth in Japanese Patent Application No. 59-268926, pages 94-95, and Japanese Patent Application Kokai No. 59-157636, page 38. They may be used alone or in combination.
To promote dye transfer, the photosensitive element or dye-fixing element may contain a hydrophilic thermal solvent which is solid at an ambient temperature, but melts at elevated temperatures to serve as solvents.
The hydrophilic thermal solvent may be incorporated in the photosensitive element and/or the dye-fixing element. Although the solvent can be incorporated into any of the emulsion layer, intermediate layer, protective layer, and dye-fixing layer, it is preferred to incorporate it into the dye-fixing layer and/or layers adjacent thereto. Examples of the hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds. A high-boiling organic solvent may be contained in the photosensitive element and/or the dyefixing element for the purpose of promoting dye transfer.
The support suitable for use in the photosensitive element and/or dye-fixing element according to the present invention must withstand the processing temperature. Exemplary of ordinary supports there may be given not only glass, paper, polymer film, metal and analogues, but also those described as supports in Japanese Patent Application No. 59-268926, pages 95-96.
In the practice of the present invention, the heat-developable photosensitive, protective, intermediate, undercoat, backcoat, dye-fixing, and other layers may be applied by any conventional coating methods, typically, the method described in U.S. Pat. No. 4,500,626.
The light source for image exposure to record an image in the heat-developable light-sensitive element may be any radiation including visible light. In general, light sources used in ordinary color printing may be used, for example, tungsten lamps, mercury lamps, halogen lamps like iodine lamps, xenon lamps, laser sources, CRT sources, fluorescent lamps, light emitting diodes (LED), and the like as set forth in Japanese Patent Application No. 59-268926, page 100 and U.S. Pat. No. 4,500,626, col. 56.
In the practice of the present invention, a heat development step and a dye transfer step may be carried out independently or concurrently. A continuous step is also contemplated herein in that development is immediately followed by dye transfer within the single step.
Representative processes are processes comprising (1) imagewise exposing a photosensitive element, heating the element, placing a dye-providing element thereon, and causing a mobile dye to transfer to the dye-providing element optionally by heating, and (2) imagewise exposing a photosensitive element, placing a dye-providing element thereon, and heating the assembly to transfer a mobile dye to to the dye-providing element. These processes (1) and (2) may be carried out in the substantial absence of water or in the presence of a minor amount of water.
The heating temperature used in the heat development step generally ranges from about 50� C. to about 250� C., preferably from about 80� C. to about 180� C. The upper limit of heating temperature is the boiling point of water when heating is effected in the presence of a minor amount of water. Where a dye transfer step is carried out after completion of a heat development step, the heating temperature used in the transfer step may range from room temperature to the temperature used in the heat development to enable dye transfer, more preferably from 50� C. to a temperature which is about 10� C. lower than the temperature used in the heat development.
In one preferred mode of the image forming process of the present invention, a heat-developable photosensitive material is heated to conduct development in the presence of a minor amount of water and a base and/or base precursor after or simultaneous with imagewise exposure, thereby transferring to the dye-fixing layer a diffusible dye which is produced in areas corresponding or counter-corresponding to silver images at the same time as development. This mode produces a high density color image within a short time because the reaction of producing or releasing the diffusible dye proceeds very quickly and hence, the migration of the diffusible dye to the dye-fixing layer takes place quickly.
The amount of water used in this image forming mode is as small as at least 1/10 of the weight of the overall coating of the photosensitive and dye-fixing elements, and preferably ranges from 1/10 of the weight of the overall coatings of the photosensitive and dye-fixing elements up to the weight of solvent corresponding to the maximum swollen volume of the overall coatings, more specifically up to the weight of solvent corresponding to the maximum swollen volume of the overall coatings minus the weight of the overall coatings.
Swollen coating films are unstable, and even susceptible to local oozing under certain conditions. To avoid such inconvenience, the amount of water should preferably be up to the weight of water corresponding to the maximum swollen volume of the overall coatings of the photosensitive and dye-fixing elements. More particularly, the amount of water ranges from 1 gram to 50 grams, more preferably from 2 grams to 35 grams, and most preferably from 3 grams to 25 grams per square meter of the combined surface area of the photosensitive and dye-fixing elements.
The base and/or base precursor used in the above-described mode may be incorporated in either the photosensitive element or the dye-fixing element. It may also be supplied as its solution in water.
Preferably in the above-described mode, a basic metal compound difficultly soluble in water and a compound (complexing compound) capable of water-mediated complexing reaction with the metal ion of the metal compound in the presence of water medium may be contained as base precursors in an image forming reaction system so that these two compounds react with each other to increase the pH of the system at the time of heating.
The term image forming reaction system used herein designates a region where image forming reaction takes place. Specifically contemplated is a layer belonging to both the photosensitive element and the dye-fixing element. When more than one such layer is present, either of them may be assigned.
The difficultly soluble metal compound and the complexing compound should be at least added to separate layers in order to prevent them from reacting until development treatment commences. For instance, in a so-called mono-sheet material wherein the photosensitive element and the dye-fixing element are on a common support, these two compounds may be added to separate layers between which at least one layer preferably intervenes. In a more preferred embodiment, the difficultly soluble metal compound and the complexing compound are separately contained in layers formed on separate supports. For example, the difficultly soluble metal compound may preferably be contained in a photosensitive element having one support and the complexing compound contained in a dye-fixing element having another support. The complexing compound may be provided in the form of a solution in water to be supplied. The difficultly soluble metal compound is desirably contained as a fine particulate dispersion prepared, for example, by the methods described in Japanese Patent Application Kokai Nos. 56-174830 and 53-102733, wherein it preferably has an average particle size of up to 50 μm, more preferably up to 5 μm. The difficultly soluble metal compound may be added to any one or more of the layers of the photosensitive element including photosensitive, intermediate, and protective layers.
The amount of the difficultly soluble metal compound and the complexing compound contained in layers on a support or supports depends on a particular type of compound used, the particle size of the difficultly soluble metal compound, complexing reaction rate, and other factors. Each of them is preferably contained in an amount of up to 50% by weight of the weight of the associated coating layer, more preferably from 0.01 to 40% by weight. Where the complexing compound is provided in the form of a solution in water, the solution preferably contains 0.005 to 5 mols, especially 0.05 to 2 mols of the complexing compound per liter of water. The content of the complexing compound in the reaction system according to the present invention is preferably 1/100 to 100 times, more preferably 1/10 to 20 times that of the difficultly soluble metal compound.
A suitable method for providing water to the photosensitive or dye-fixing layer is the method described in Japanese Patent Application No. 59-268926, pages 101-102, for example.
Heating means used during the development or transfer step in the practice of the present invention may be any of the means described in Japanese Patent Application No. 59-268926, pages 102-103, including heat blocks, irons, and heat rollers. It is also possible to provide the photosensitive and/or dye-fixing element with a layer of electroconductive material such as graphite, carbon black, and metal whereby electric current is conducted to the conductive layer to directly heat the associated elements.
The pressure under which the photosensitive and dye-fixing layers are in firm contact and application of such pressure may be in accord with the method described in Japanese Patent Application No. 59-268926, pages 103-104.
In the treatment of a photographic element according to the present invention, any of various well-known heat-development equipment may be used. Useful equipment are described in, for example, Japanese Patent Application Kokai Nos. 59-75247, 59-177547, 59-181353, and 60-18951, and Japanese Utility Model Application No. 60-116734.
In the image forming process including heating step according to the present invention, there are contemplated two representative embodiments, one embodiment wherein heat development is conducted in the presence of water and a base and/or base precursor and another embodiment wherein heat development is conducted in the substantial absence of water. Although both of them perform well, the former embodiment is more desirable for some reasons. The presence of water is more advantageous to facilitate the reaction. The 1-phenyltetrazole ring contained in useful representative compounds among the compounds of general formula (I) is generally sensitive to heat, and the former embodiment can employ a lower treating temperature.
In the more preferred former embodiment, either of the following two methods may preferably be employed, a first method of incorporating a base or analogue in the dye-fixing element and a second method of separately adding the difficultly soluble metal compound and the complexing compound to the photosensitive element and the dye-fixing element, respectively. The compound of general formula (I) may preferably be added to the photosensitive element in the first method, and either the photosensitive element or the dye-fixing element in the second method.
The development retarder released from the compound of general formula (I) should preferably have appropriate diffusibility when the compound is added to the dye-fixing element, but contrarily, should preferably have poor diffusibility when the compound is added to the photosensitive element. More illustratively, as previously described, the most preferred development retarders are ##STR26## wherein R1 preferably contains up to 9 carbon atoms when the precursor compound is added to the dye-fixing element, and at least 5 carbon atoms, especially at least 10 carbon atoms when the precursor compound is added to the photosensitive element. The most useful embodiment prefers the use of the second method and the addition of a precursor of a poorly difffusible development retarder to the photosensitive layer although substantially equivalent effect is accomplished in other embodiments.
Since a heat-developable photosensitive material is heated in the presence of a compound of general formula (I) in the image forming process including heating step according to the present invention, the development process terminates at an optimum degree of development to avoid fogging due to over-development and minimize photographic performance variation due to varying heating temperature.
A silver benzotriazole emulsion was prepared as follows. Twenty eight (28) grams of gelatin and 13.2 grams of benzotriazole were dissolved in 300 ml of water. The resulting solution was agitated at 40� C. A solution of 17 grams silver nitrate in 100 ml water was added to the solution over a period of 2 minutes.
An aqueous gelatin solution was prepared by dissolving 20 grams of gelatin and 3 grams of sodium chloride in 1000 ml of water and kept at a temperature of 75� C. While fully agitating the gelatin solution, 600 ml of an aqueous solution of sodium chloride and potassium bromide and another aqueous solution of 0.59 mols of silver nitrate in 600 ml of water were concurrently added to the gelatin solution at an equal flow rate over a period of 40 minutes. In this way, there was prepared a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.35 μm (bromine 80 mol%).
Five (5) grams of yellow dye-providing substance (A) having the formula shown below was dissolved together with 0.5 grams of succinic acid-2-ethylhexyl ester sodium sulfonate and 10 grams of triisononyl phosphate in 30 ml of ethyl acetate by heating at about 60� C., obtaining a homogeneous solution. The solution was mixed with 100 grams of a 10 wt% lime-treated gelatin solution by agitation, and the mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called yellow dye-providing substance dispersion.
A gelatin dispersion of compound No. 129 of the present invention was prepared as follows.
To 100 grams of an aqueous solution of 1% gelatin were added 5 grams of compound No. 129 and 0.5 grams of a surface-active agent of the following formula: ##STR27## The mixture was ground for 10 minutes in a ball mill filled with 100 grams of glass beads having an average diameter of about 0.6 mm. Filtration of the glass beads resulted in a gelatin dispersion of compound No. 129.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 101
hardener*3 (coating weight 20 mg/m2)
silver chlorobromide emulsion (bromine 50 mol%,
sulfamide compound*6 (coating weight 180 mg/m2)
compound No. 129 (coating weight 12 mg/m2)
yellow dye-providing substance (A) (coating weight 500 mg/m2)
silver chlorobromide emulsion (bromine 80 mol%,
coating weight 300 mg/m2 of Ag)
magenta dye-providing substance (B) (coating weight 320 mg/m2)
cyan dye-providing substance (C) (coating weight 320 mg/m2)
Support (polyethylene terephthaIate 100 μm thick) ##STR28##
Photosensitive material Nos. 102 and 103 were prepared by following the same procedure as photosensitive material No. 101 except that compound No. 129 was replaced by compound Nos. 117 and 116 according to the present invention. For comparison purpose, photosensitive material No. 104 was prepared by following the same procedure as photosensitive material No. 101 except that the compound of the present invention was omitted.
In 200 ml of water was dissolved 15 grams of a polymer having the structure as defined below. The solution was homogeneously mixed with 100 grams of 10 wt% lime-treated gelatin and 7 grams of guanidine carbonate. The resulting mixture was uniformly spread onto a paper substrate laminated with polyethylene having titanium dioxide dispersed therein, thereby forming a dye-fixing layer having a uniform wet thickness of 85 μm, which was then dried.
Separately, 0.75 grams of gelatin hardener H-1, 0.25 grams of gelatin hardener H-2, 160 ml of water, and 100 grams of 10% lime-treated gelatin were evenly mixed. The mixture was uniformly coated on the dye-fixing layer to a wet film thickness of 60 μm. After drying, there was obtained a dye-fixing material. ##STR29## (intrinsic viscosity 0.3473 as measured in 1/20 M Na2 HPO4 aqueous solution at 30� C.)
CH2 =CHSO2 CH2 CONHCH2 CH2 NHCOCH2 SO2 CH=CH2 Gelatin hardener H-2:
CH2 =CHSO2 CH2 CONHCH2 CH2 CH2 NHCOCH2 SO2 CH=CH2 Multilayered color light-sensitive material Nos. 101-104 were exposed for one second at 500 lux under a tungsten lamp through three color separation filters G, R, and IR having a continuously varying density. It should be noted that filter G is a 500-600 nm band pass filter, filter R is a 600-700 nm band pass filter, and filter IR is a filter transmitting light having wavelengths of at least 700 nm.
Water was applied by means of a wire bar in an amount of 20 ml per square meter to the emulsion surface of the thus exposed light-sensitive material, which was superimposed on the dye-fixing material such that their effective surfaces faced one another. After heating for 20 seconds through heat rollers at such a temperature such that the temperature of the wet film reached 93� or 98� C., the dye-fixing material was peeled from the light-sensitive material. The dye-fixing material then bore thereon clear images of yellow (Y), magenta (M), and cyan (C) corresponding to the three color separation filters. The maximum density (Dmax) and minimum density (Dmin) of the respective color images were measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 1.
TABLE 1______________________________________  Com-          Heating     HeatingPhoto- pound         at 93� C.                            at 98� C.sensitive  of            for 20 sec. for 20 sec.material  invention     Dmax    Dmin  Dmax  Dmin______________________________________101    129      Yellow   1.86  0.11  1.91  0.13           Magenta  2.03  0.13  2.08  0.15           Cyan     2.14  0.12  2.17  0.16102    117      Yellow   1.83  0.12  1.88  0.18           Magenta  2.02  0.12  2.06  0.17           Cyan     2.12  0.11  2.14  0.14103    116      Yellow   1.88  0.14  1.92  0.18           Magenta  2.04  0.13  2.10  0.20           Cyan     2.17  0.13  2.20  0.19104    --       Yellow   1.84  0.12  1.96  0.40(control)       Magenta  2.02  0.14  2.18  0.35           Cyan     2.15  0.12  2.21  0.28______________________________________
As evident from the data in Table 1, the photosensitive materials containing the compounds of the present invention experience a smaller increase of Dmax and Dmin when the developing temperature is raised by 5 degrees whereas the control material free of the compound of the present invention produces markedly increased fog. It is thus evident that the compounds of the present invention have great temperature compensation effect.
A gelatin dispersion of basic zinc carbonate was prepared.
Combined with 4% aqueous gelatin solution were 12.5 grams of basic zinc carbonate and 2 grams of a surface-active agent of the formula: ##STR30##
The mixture was ground for 30 minutes in a ball mill filled with glass beads having an average diameter of 0.75 mm. Filtration of the glass beads resulted in a gelatin dispersion of basic zinc carbonate.
Using this dispersion as well as the emulsions, dye-providing substances, and additives described in Example 1, photosensitive material No. 121 was prepared as formulated below.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 121
basic zinc carbonate (coating weight 800 mg/m2)
sensitizing dye D-3 (coating weight 10-8 mol/m2) hardener*3 (coating weight 16 mg/m2)
Support (polyethylene terephthalate 100 μm thick)
Note: The asterisked substances (*1-6) and other substances are the same as in Formulation of Example 1.
First, 15 grams of the polymer used in preparing the dye-fixing material of Example 1 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin, 8 grams of compound (a) of the following formula, and 3 grams of a gelatin dispersion of compound No. 105 of the present invention dispersed by the same method as in Example 1. ##STR31##
The mixture was evenly spread on a paper substrate laminated with polyethylene having titanium dioxide dispersed therein, thereby forming a dye-fixing layer having a uniform wet thickness of 85 μm, which was then dried.
Separately, 0.75 grams of gelatin hardener H-1, 0.25 grams of gelatin hardener H-2, 160 ml of water, and 100 grams of 10% lime-treated gelatin were evenly mixed. The mixture was uniformly coated on the dye-fixing layer to a wet film thickness of 60 μm. After drying, there was obtained a dye-fixing material.
Using photosensitive material No. 121 and the above prepared dye-fixing material, the procedure of Example 1 was followed. The results are shown below.
TABLE 2______________________________________Photosensitive material No. 121    Heating at 93� C.                 Heating at 98� C.    for 20 sec.  for 20 sec.    Dmax  Dmin       Dmax    Dmin______________________________________Yellow     1.95    0.12       2.01  0.16Magenta    2.04    0.14       2.09  0.19Cyan       2.18    0.11       2.20  0.14______________________________________
As seen from the data of Table 2, the compound of the present invention has an enhanced temperature compensation effect.
A gelatin dispersion of zinc hydroxide was prepared.
Combined with 12.5 grams of zinc hydroxide were 0.5 grams of carboxymethyl cellulose and 4% aqueous gelatin solution. The mixture was milled for 30 minutes in a ball mill filled with glass beads having an average diameter of 0.75 mm. Filtration of the glass beads resulted in a gelatin dispersion of zinc hydroxide.
A dispersion of compound No. 113 of the present invention was prepared by following the procedure of Example 1.
Using the gelatin dispersion and compound No. 113 dispersion prepared above as well as the emulsions, dye-providing substances, and additives described in Example 1, a photosensitive material No. 131 of the following formulation was prepared.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 131
sensitizing dye D-1 (coating weight 10-6 mol/m2) compound No. 113 (coating weight 10 mg/m2)
zinc hydroxide (coating weight 300 mg/m2)
compound No. 113 (coating weight 10 mg/m2)
Note: The asterisked substances (*1 -6) and other substances are the same as in Formulation of Example 1.
Photosensitive material Nos. 132 and 133 were prepared by following the same procedure as photosensitive material No. 131 except that compound No. 113 was replaced by compound Nos. 127 and 131 according to the present invention. For comparison purpose, photosensitive material No. 134 was prepared by following the same procedure as photosensitive material No. 131 except that the compound of the present invention was replaced by the compound (b) described in Japanese Patent Publication No. 60-19498 and having the formula: ##STR32##
First, 15 grams of the polymer used in preparing the dye-fixing material of Example 1 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin and 10 grams of compound (a) used in Example 2.
Using photosensitive material Nos. 131-134 and the above-prepared dye-fixing material, the procedure of Example 1 was followed. The results are shown below.
TABLE 3______________________________________  Com-              Heating   HeatingPhoto- pound             at 90� C.                              at 95� C.sensitive  of       Color    for 25 sec.                              for 25 sec.material  invention           image    Dmax  Dmin  Dmax  Dmin______________________________________131    113      Yellow   1.95  0.13  2.01  0.16           Magenta  2.04  0.14  2.08  0.17           Cyan     2.18  0.13  2.24  0.15132    127      Yellow   1.87  0.12  1.93  0.15           Magenta  2.02  0.12  2.06  0.16           Cyan     2.15  0.14  2.19  0.18133    131      Yellow   1.89  0.12  1.95  0.14           Magenta  2.10  0.11  2.14  0.14           Cyan     2.13  0.14  2.18  0.17134    (b)      Yellow   1.52  0.12  1.68  0.20(compari-       Magenta  1.84  0.14  1.98  0.24son)            Cyan     2.01  0.19  2.04  0.27______________________________________
As evident from the data of Table 3, the compounds of the present invention have greater temperature compensation effect than the compound described in Japanese Patent Publication No. 60-19498.
A silver iodobromide emulsion was prepared.
In 3000 ml of water were dissolved 40 grams of gelatin and 26 grams of KBr. The solution was agitated while being kept at 50� C. A solution of 34 grams of silver nitrate in 200 ml of water was then added to the solution over 10 minutes. Thereafter, a solution of 3.3 grams of KI in 100 ml of water was added over 2 minutes. The resulting silver iodobromide emulsion was adjusted to such a pH that an excess salt precipitated, and the excess salt was filtered off. The emulsion was then adjusted to pH 6.0, obtaining a silver iodobromide emulsion in a yield of 400 grams.
A gelatin dispersion of a dye-providing substance was prepared by the same procedure as in Example 1 except that 7.5 grams of tricresyl phosphate was replaced by 10 grams of triisononyl phosphate as the solvent in the dispersion of the magenta dye-providing substance and the dye-providing substance (C) was replaced by a dye-providing substance (D) as defined below in the dispersion of the cyan dye-providing substance. ##STR33##
A gelatin dispersion of compound No. 101 of the present invention was prepared by the same procedure as in Example 1.
Using these preparations, there was prepared a color light-sensitive material No. 141 of multi-layer structure as shown in the following formulation:
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 141
base precursor*3 (coating weight 220 mg/m2)
compound No. 101 (coating weight 10 mg/m2)
silver iodobromide emulsion (iodine 10 mol%, coating
weight 400 mg/m2 of Ag)
sulfamide compound*4 (coating weight 180 mg/m2)
base precursor*3 (coating weight 520 mg/m2)
high-boiling solvent*1 (coating weight 800 mg/m2)
sensitizing dye D-1 (coating weight 10-8 mol/m2)
base precursor*3 (coating weight 515 mg/m2)
base precursor*3 (coating weight 230 mg/m2)
cyan dye-providing substance (D) (coating weight 300 mg/m2)
Support (polyethylene terephthalate 100 μm thick) ##STR34##
First, 0.75 grams of gelatin hardener H-1, 0.25 grams of gelatin hardener H-2, 160 ml of water, and 100 grams of 10% lime-treated gelatin were evenly mixed. The mixture was uniformly spread on a paper substrate laminated with polyethylene having titanium dioxide dispersed therein to a wet thickness of 60 μm and then dried.
Separately, 15 grams of the polymer used in preparing the dye-fixing material of Example 1 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin. The mixture was evenly spread on the coating to a uniform wet thickness of 85 μm and then dried, obtaining a dye-fixing material.
The color light-sensitive material of the above-formulated multi-layer structure was exposed for 10 seconds at 2000 lux under a tungsten lamp through three color separation filters B, G, and R having a continuously varying density, and then evenly heated for 20 seconds on a heat block heated at 150� C. or 153� C.
The dye-fixing material dipped in water. The heated light-sensitive material was placed on the wet dye-fixing material such that their effective surfaces faced one another. After heating for 6 seconds on a heat block at 80� C., the dye-fixing material was peeled from the light-sensitive material whereupon the dye-fixing material bore a negative magenta image thereon. Then density of the negative image was measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 4.
TABLE 4______________________________________Photosensitive material No. 141   Heating at 150� C.                Heating at 153� C.   for 20 sec.  for 20 sec.   Dmax  Dmin       Dmax    Dmin______________________________________Yellow    1.92    0.16       1.98  0.19Magenta   2.04    0.14       2.09  0.20Cyan      2.07    0.17       2.12  0.19______________________________________
As seen from the data of Table 4, the compound of the present invention has an enhanced temperature compensation effect.
An aqueous gelatin solution was prepared by dissolving 20 grams of gelatin and 3 grams of sodium chloride in 1000 ml of water and kept at a temperature of 75� C. While fully agitating the gelatin solution, 600 ml of an aqueous solution of sodium chloride and potassium bromide and another aqueous solution of 0.59 mols of silver nitrate in 600 ml of water were concurrently added to the gelatin solution at an equal flow rate over a period of 40 minutes. In this way, there was prepared a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.40 μm (bromine 50 mol%).
Next, a dispersion of a dye-providing substance in gelatin was prepared as follows. Yellow, magenta, and cyan dye-providing substances (A), (B), and (C) are the same as used in Example 1.
Five (5) grams of yellow dye-providing substance (A) was dissolved together with 0.5 grams of succinic acid-2-ethylhexyl ester sodium sulfonate and 10 grams of triisononyl phosphate in 30 ml of ethyl acetate by heating at about 60� C., obtaining a homogeneous solution. The solution was mixed with 30 grams of a 10 wt% lime-treated gelatin solution by agitation, and the mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called yellow dye-providing substance dispersion.
A magenta dye-providing substance dispersion was prepared by the same procedure as above except that magenta dye-providing substance (B) was used as the dye-providing substance and 7.5 grams of tricresyl phosphate was used as the high boiling solvent.
A cyan dye-providing substance dispersion was prepared by the same procedure as above except that cyan dye-providing substance (C) was used as the dye-providing substance.
A gelatin dispersion of compound No. 205 of the present invention was prepared as follows.
To 100 grams of an aqueous solution of 1% gelatin were added 5 grams of compound No. 205 and 0.5 grams of a surface-active agent of the following formula: ##STR35## The mixture was ground for 10 minutes in a ball mill filled with 100 grams of glass beads having an average diameter of about 0.6 mm. Filtration of the glass beads resulted in a gelatin dispersion of compound No. 205.
Using these preparations, there was prepared a color light-sensitive material No. 201 of multi-layer structure as shown in the following formulation:
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 201
compound No. 205 (coating weight 15 mg/m2)
Support (polyethylene terephthalate 100 μm thick) ##STR36## Dye-providing substances (A), (B), and (C), and sensitizing dyes D-1, D-2, and D-3 are the same as in Example 1.
Photosensitive material Nos. 202 and 203 were prepared by following the same procedure as photosensitive material No. 201 except that compound No. 205 was replaced by compound Nos. 210 and 220 according to the present invention. For comparison purpose, photosensitive material No. 204 was prepared by following the same procedure as photosensitive material No. 201 except that the compound of the present invention was omitted.
Separately, 0.75 grams of gelatin hardener H-1, 0.25 grams of gelatin hardener H-2, 160 ml of water, and 100 grams of 10% lime-treated gelatin were evenly mixed. The mixture was uniformly coated on the dye-fixing layer to a wet film thickness of 60 μm. After drying, there was obtained a dye-fixing material. ##STR37## (intrinsic viscosity 0.3473 as measured in 1/20 M Na2 HPO4 aqueous solution at 30� C.)
CH2 ═CHSO2 CH2 CONHCH2 CH2 NHCOCH2 SO2 CH═CH2 Gelatin hardener H-2:
CH2 ═CHSO2 CH2 CONHCH2 CH2 CH2 NHCOCH2 SO2 CH═CH2 Multilayered color light-sensitive material Nos. 201-204 were exposed for one second at 500 lux under a tungsten lamp through three color separation filters G, R, and IR having a continuously varying density. It should be noted that filter G is a 500-600 nm band pass filter, filter R is a 600-700 nm band pass filter, and filter IR is a filter transmitting light having wavelengths of at least 700 nm.
Water was applied by means of a wire bar in an amount of 20 ml per square meter to the emulsion surface of the thus exposed light-sensitive material, which was superimposed on the dye-fixing material such that their effective surfaces faced one another. After heating for 20 seconds through heat rollers at such a temperature such that the temperature of the wet film reached 93� or 98� C., the dye-fixing material was peeled from the light-sensitive material. The dye-fixing material then bore thereon clear images of yellow (Y), magenta (M), and cyan (C) corresponding to the three color separation filters. The maximum density (Dmax) and minimum density (Dmin) of the respective color images were measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 5.
TABLE 5______________________________________  Com-              Heating   HeatingPhoto- pound    at       93� C.                              at 98� C.sensitive  of                for 20 sec.                              for 20 sec.material  invention         Dmax  Dmin  Dmax  Dmin______________________________________201    129      Yellow   1.80  0.11  1.84  0.17           Magenta  2.03  0.12  2.07  0.14           Cyan     2.12  0.14  2.15  0.19202    117      Yellow   1.78  0.10  1.82  0.14           Magenta  2.00  0.11  2.03  0.13           Cyan     2.08  0.12  2.14  0.16203    116      Yellow   1.84  0.13  1.89  0.20           Magenta  2.01  0.14  2.07  0.19           Cyan     2.13  0.12  2.18  0.20204    --       Yellow   1.84  0.12  1.96  0.40(control)       Magenta  2.02  0.14  2.18  0.35           Cyan     2.15  0.12  2.21  0.28______________________________________
As evident from the data in Table 5, the photosensitive materials containing the compounds of the present invention experience a smaller increase of Dmax and Dmin when the developing temperature is raised by 5 degrees whereas the control material free of the compound of the present invention produces markedly increased fog. It is thus evident that the compounds of the present invention have great temperature compensation effect.
Combined with 4% aqueous gelatin solution were 12.5 rams of zinc hydroxide and 2 grams of a surface-active agent of the formula: ##STR38##
The mixture was ground for 30 minutes in a ball mill filled with glass beads having an average diameter of 0.75 mm. Filtration of the glass beads resulted in a gelatin dispersion of zinc hydroxide.
Using this dispersion as well as the emulsions, dye-providing substances, and additives described in Example 5, photosensitive material No. 221 was prepared as formulated below.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 221
zinc hydroxide (coating weight 800 mg/m2)
Note: The asterisked substances (*1-6) and other substances are the same as in Formulation of Example 5.
First, 15 grams of the polymer used in preparing the dye-fixing material of Example 5 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin, 8 grams of compound (a) of the following formula, and 3 grams of a gelatin dispersion of compound No. 205 of the present invention dispersed by the same method as in Example 5. ##STR39##
Using photosensitive material No. 221 and the above prepared dye-fixing material, the procedure of Example 5 was followed. The results are shown below.
TABLE 6______________________________________Photosensitive material No. 221    Heating at 93� C.                 Heating at 98� C.    for 20 sec.  for 20 sec.    Dmax  Dmin       Dmax    Dmin______________________________________Yellow     2.04    0.12       2.08  0.18Magenta    2.08    0.14       2.12  0.17Cyan       2.20    0.16       2.26  0.19______________________________________
As seen from the data of Table 6, the compound of the present invention has an enhanced temperature compensation effect.
A dispersion of a dye-providing substance in gelatin was prepared as follows. Dye-providing substances (A), (B), and (C) are the same as used in Example 1.
Five (5) grams of yellow dye-providing substance (A) was dissolved together with 0.5 grams of succinic acid-2ethylhexyl ester sodium sulfonate, 2.5 grams of triisononyl phosphate, and 0.1 gram of a mercapto compound having the formula (c): ##STR40## in 30 ml of ethyl acetate by heating at about 60� C., obtaining a homogeneous solution. The solution was mixed with 100 grams of a 10 wt% lime-treated gelatin solution by agitation, and the mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called yellow dye-providing substance dispersion.
A dispersion of compound No. 227 of the present invention was prepared by following the procedure of Example 5.
Using the dispersions of the dye-providing substances and compound No. 227 prepared above as well as the gelatin dispersion of zinc hydroxide described in Example 6, the emulsions and additives described in Example 5, a photosensitive material No. 231 of the following formulation was prepared.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 231
hardener 3 (coating weight 20 mg/m2)
mercapto compound*6 (coating weight 180 mg/m2)
compound No. 227 (coating weight 8 mg/m2)
Support (polyethylene terephthalate 100 μm thick) ##STR41##
Photosensitive material Nos. 232 and 233 were prepared by following the same procedure as photosensitive material No. 231 except that compound No. 227 was replaced by compound Nos. 234 and 205 according to the present invention. For comparison purpose, photosensitive material No. 234 was prepared by following the same procedure as photosensitive material No. 231 except that the compound of the present invention was omitted.
First, 15 grams of the polymer used in preparing the dye-fixing material of Example 5 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin and 10 grams of compound (a) of the following formula: ##STR42##
Multilayered color light-sensitive material Nos. 231234 were exposed for one second at 500 lux under a tungsten lamp through three color separation filters G, R, and IR having a continuously varying density. It should be noted that filter G is a 500-600 nm band pass filter, filter R is a 600-700 nm band pass filter, and filter IR is a filter transmitting light having wavelengths of at least 700 nm.
Water was applied by means of a wire bar in an amount of 20 ml per square meter to the emulsion surface of the thus exposed light-sensitive material, which was superimposed on the dye-fixing material such that their effective surfaces faced one another. After heating for 25 seconds through heat rollers at such a temperature such that the temperature of the wet film reached 90� or 95� C., the dye-fixing material was peeled from the light-sensitive material. The dye-fixing material then bore thereon clear images of yellow (Y), magenta (M), and cyan (C) corresponding to the three color separation filters. The maximum density (Dmax) and minimum density (Dmin) of the respective color images were measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 7.
TABLE 7______________________________________  Com-              Heating   HeatingPhoto- pound             at 90� C.                              at 95� C.sensitive  of       Color    for 25 sec.                              for 25 sec.material  invention           image    Dmax  Dmin  Dmax  Dmin______________________________________231    227      Yellow   2.02  0.16  2.06  0.19           Magenta  2.00  0.17  2.04  0.19           Cyan     2.23  0.15  2.27  0.18232    234      Yellow   1.98  0.18  2.03  0.20           Magenta  2.01  0.17  2.06  0.19           Cyan     2.12  0.14  2.18  0.17233    205      Yellow   1.76  0.15  1.80  0.17           Magenta  1.93  0.15  1.98  0.18           Cyan     2.05  0.14  2.09  0.17234    --       Yellow   2.04  0.18  2.15  0.30(compari-       Magenta  2.02  0.19  2.11  0.29son)            Cyan     2.24  0.14  2.31  0.31______________________________________
As evident from the data of Table 7, the compounds of the present invention have great temperature compensation effect.
A gelatin dispersion of a dye-providing substance was prepared by the same procedure as in Example 5 except that 7.5 grams of tricresyl phosphate was replaced by 10 grams of triisononyl phosphate as the solvent in the dispersion of the magenta dye-providing substance and the dye-providing substance (C) was replaced by a dye-providing substance (D) as defined below in the dispersion of the cyan dye-providing substance. ##STR43##
A gelatin dispersion of compound No. 205 of the present invention was prepared by the same procedure as in Example 5.
Using these preparations, there was prepared a color light-sensitive material No. 241 of multi-layer structure as shown in the following formulation:
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 241
compound No. 205 (coating weight 10 mg/m2)
silver iodobromide emulsion (iodine 10 mol % coating weight 400 mg/m2 of Ag)
silver iodobromide emulsion (iodine 10 mol %, coating weight 400 mg/m2 of Ag)
sensitizing dye D-1 (coating weight 108 mol/m2)
base precursor*3 (coating weight 515 mg/m2) magenta dye-providing substance (B) (coating weight 400 mg/m2)
sulfamide compound*4 (coating weight 180 mg/m2) sensitizing dye D-2 (coating weight 8�10-7 mol/m2)
Support (polyethylene terephthalate 100 μm thick) ##STR44##
Separately, 15 grams of the polymer used in preparing the dye-fixing material of Example 5 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin. The mixture was evenly spread on the coating to a uniform wet thickness of 85 μm and then dried, obtaining a dye-fixing material.
The color light-sensitive material of the aboveformulated multi-layer structure was exposed for 10 seconds at 2000 lux under a tungsten lamp through three color separation filters B, G, and R having a continuously varying density, and then evenly heated for 20 seconds on a heat block heated at 150� C. or 153� C.
The dye-fixing material was dipped in water. The heated light-sensitive material was placed on the wet dyefixing material such that their effective surfaces faced one another. After heating for 6 seconds on a heat block at 80� C., the dye-fixing material was peeled from the light-sensitive material whereupon the dye-fixing material bore a nagative magenta image thereon. The density of the nagative image was measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 8.
TABLE 8______________________________________Photosensitive material No. 241   Heating at 150� C.                 Heating at 153� C.   for 20 sec.   for 20 sec.   Dmax  Dmin        Dmax    Dmin______________________________________Yellow    1.90    0.18        1.92   0.22Magenta   2.02    0.17        2.04  0.19Cyan      2.08    0.19        2.12  0.21______________________________________
As seen from the data of Table 8, the compound of the present invention has an enhanced temperature compensation effect.
Preparation of Silver Acetylene Dispersion
In 1000 ml of water and 200 ml of ethanol were dissolved 20 grams of gelatin and 4.6 grams of 4-acetylaminophenyl acetylene. The solution was agitated at 40� C.
To the solution was added 4.5 grams of silver nitrate in 200 ml of water over a period of 5 minutes. The dispersion was adjusted to such pH that an excess salt precipitated. The excess salt was filtered off, and the dispersion was adjusted to pH 6.3, obtaining a silver acetylene dispersion in a yield of 400 grams.
A silver benzotriazole emulsion was prepared by dissolving 28 grams of gelatin and 13.2 grams of benzotriazole in 300 ml of water. The solution was agitated at 40� C. A solution of 17 grams silver nitrate in 100 ml water was added to the solution over a period of 2 minutes.
After water rinsing and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7tetraazaindene were added to effect chemical sensitization at 60� C. There was obtained an emulsion in a yield of 600 grams.
Next, a dispersion of a dye-providing substance in gelatin was prepared as follows. Dye-providing substances (A), (B), and (C) are the same as used in Example 1.
Five (5) grams of yellow dye-providing substance (A) was dissolved together with 0.5 grams of succinic acid-2-ethylhexyl ester sodium sulfonate, 5 grams of triisononyl phosphate, and 0.2 grams of a reducing agent of the following formula in 30 ml of ethyl acetate by heating at about 60� C., obtaining a homogeneous solution. The solution was mixed with 100 grams of a 10 wt % lime-treated gelatin solution by agitation, and the mixture was dispersed with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called yellow dye-providing substance dispersion. ##STR45##
A gelatin dispersion of compound No. 315 of the present invention was prepared as follows.
To 100 grams of an aqueous solution of 1% gelatin were added 5 grams of compound No. 315 and 0.5 grams of a surface-active agent of the following formula: ##STR46## The mixture was ground for 10 minutes in a ball mill filled with 100 grams of glass beads having an average diameter of about 0.6 mm. Filtration of the glass beads resulted in a gelatin dispersion of compound No. 315 (average particle size 0.5 μm).
A gelatin dispersion of zinc hydroxide was prepared by combining 12.5 grams of zinc hydroxide and 1 gram of carboxymethyl cellulose with 4% aqueous gelatin solution. The mixture was milled for 30 minutes in a mill filled with glass beads having an average diameter of 0.75 mm.
Filtration of the glass beads resulted in a gelatin dispersion of zinc hydroxide (average particle size 0.3 μm).
Using these preparations, there was prepared a color light-sensitive material No. 301 of multi-layer structure as shown in the following formulation:
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 301
gelatin (coating weight 100 mg/m2)
compound No. 315 (coating weight 10 mg/m2)
sulfamide compound*6 (coating weight 20 mg/m2)
silver acetylene (coating weight 50 mg/m2 of Ag)
zinc hydroxide (coating weight 200 mg/m2)
gelatin (coating weight 600 mg/m2)
silver chlorobromide emulsion (bromine 80 mol %,
sulfamide compound*6 (coating weight 13 mg/m2)
silver benzotriazole emulsion (coating weight 20 mg/m2 of Ag)
silver acetylene (coating weight 50 mg/m of Ag)
compound No. 315 (coating weight 12 mg/m2)
Support (polyethylene terephthalate 100 μm thick) ##STR47##
Photosensitive material Nos. 302 and 303 were prepared by following the same procedure as photosensitive material No. 301 except that compound No. 315 was replaced by compound Nos. 331 and 339 according to the present invention. For comparison purpose, photosensitive material No. 304 was prepared by following the same procedure as photosensitive material No. 301 except that the compound of the present invention was omitted, and another photosensitive material No. 305 was prepared by the same procedure except that the compound of the present invention was replaced by a compound (d) which releases phenylmercaptotetrazole having an unsubstituted benzene ring and is represented by the following formula: ##STR48##
In 200 ml of water was dissolved 15 grams of a polymer having the structure as defined below. The solution was homogeneously mixed with 100 grams of 10 wt % lime-treated gelatin and 9 grams of guanidine picolinate. The resulting mixture was uniformly spread onto a paper substrate laminated with polyethylene having titanium dioxide dispersed therein, thereby forming a dye-fixing layer having a uniform wet thickness of 85 μm, which was then dried.
Separately, 0.75 grams of gelatin hardener H-1, 0.25 grams of gelatin hardener H-2, 160 ml of water, and 100 grams of 10% lime-treated gelatin were evenly mixed. The mixture was uniformly coated on the dye-fixing layer to a wet film thickness of 60 μm. After drying, there was obtained a dye-fixing material. ##STR49## (intrinsic viscosity 0.3473 as measured in 1/20M Na2 HPO4 aqueous solution at 30� C.)
CH2 ═CHSO2 CH2 CONHCH2 CH2 CH2 NHCOCH2 SO2 CH═CH2 Multilayered color light-sensitive material Nos. 301-305 were exposed for one second at 500 lux under a tungsten lamp through three color separation filters G, R, and IR having a continuously varying density. It should be noted that filter G is a 500-600 nm band pass filter, filter R is a 600-700 nm band pass filter, and filter IR is a filter transmitting light having wavelengths of at least 700 nm.
Water was applied by means of a wire bar in an amount of 10 ml per square meter to the emulsion surface of the thus exposed light-sensitive material, which was superimposed on the dye-fixing material such that their effective surfaces faced one another. After heating for 25 seconds through heat rollers at such a temperature such that the temperature of the wet film reached 90� or 95� C., the dyefixing material was peeled from the light-sensitive material. The dye-fixing material then bore thereon clear images of yellow (Y), magenta (M), and cyan (C) corresponding to the three color separation filters. The maximum density (Dmax) and minimum density (Dmin) of the respective color images were measured by means of a Macbeth (RD-519) reflection densitometer. The results are shown in Table 9.
TABLE 9______________________________________  Com-              Heating   HeatingPhoto- pound             at 90� C.                              at 95� C.sensitive  of                for 25 sec.                              for 25 sec.material  invention         Dmax  Dmin  Dmax  Dmin______________________________________301    315      Yellow   2.12  0.15  2.16  0.17           Magenta  2.15  0.14  2.19  0.17           Cyan     2.20  0.14  2.24  0.16302    331      Yellow   2.10  0.15  2.14  0.17           Magenta  2.15  0.16  2.20  0.20           Cyan     2.23  0.15  2.28  0.18303    339      Yellow   2.09  0.16  2.12  0.20           Magenta  2.10  0.16  2.14  0.19           Cyan     2.20  0.15  2.23  0.17304    --       Yellow   2.14  0.17  2.25  0.32(control)       Magenta  2.18  0.15  2.24  0.36           Cyan     2.23  0.15  2.38  0.28305    (d)      Yellow   1.82  0.20  2.03  0.26(compari-       Magenta  1.90  0.18  2.07  0.25son)            Cyan     2.01  0.19  2.15  0.22______________________________________
As evident from the data in Table 9, the photosensitive materials containing the compounds of the present invention experience a smaller increase of Dmax and Dmin when the developing temperature is raised by 5 degrees. The control material free of the compound of the present invention produces markedly increased fog. The comparative material containing compound (d) is increased in both fog and fog increase as compared with the present materials. It is thus evident that the compounds of the present invention have great temperature conpensation effect.
This example illustrates a dye-fixing element having added thereto a compound falling within the scope of the invention.
A gelatin dispersion of basic zinc carbonate was prepared by combining 4% aqueous gelatin solution with 12.5 grams of basic zinc carbonate and 2 grams of a surface-active agent of the formula: ##STR50## The mixture was ground for 30 minutes in a ball mill filled with glass beads having an average diameter of 0.75 mm. Filtration of the glass beads resulted in a gelatin dispersion of basic zinc carbonate.
Using this dispersion as well as the emulsions, dye-providing substances, and additives described in Example 9, photosensitive material No. 321 was prepared as formulated below.
FORMULATION OF PHOTOSENSITIVE MATERIAL NO. 321
basic zinc carbonate (coating weight 600 mg/m2)
silver benzotriazole emulsion (coating weight 10 mg/m2 of Ag)
silver acetylene (coating weight 50 mg/m2)
Note: The asterisked substances (*1-6) and other substances are the same as in Formulation of Example 9.
First, 15 grams of the polymer used in preparing the dye-fixing material of Example 9 was dissolved in 200 ml of water and then combined with 100 grams of 10% lime-treated gelatin, 8 grams of guanidine picolinate, and 30 grams of a gelatin dispersion of compound No. 315 of the present invention dispersed by the same method as in Example 9.
Using photosensitive material No. 321 and the aboveprepared dye-fixing material, the procedure of Example 9 was followed. The results are shown below.
TABLE 10______________________________________Photosensitive material No. 321   Heating at 90� C.                Heating at 95� C.   for 25 sec.  for 25 sec.   Dmax  Dmin       Dmax    Dmin______________________________________Yellow    1.98    0.13       2.02  0.15Magenta   2.12    0.15       2.15  0.17Cyan      2.24    0.16       2.27  0.20______________________________________
As seen from the data of Table 10, the compound of the present invention has an enhanced temperature compensation effect.
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