US3380829A - Photographic developing compositions - Google Patents
Photographic developing compositions Download PDFInfo
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- US3380829A US3380829A US391740A US39174064A US3380829A US 3380829 A US3380829 A US 3380829A US 391740 A US391740 A US 391740A US 39174064 A US39174064 A US 39174064A US 3380829 A US3380829 A US 3380829A
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- hardening
- dioxane
- dihydroxy
- photographic
- developer
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- 239000000203 mixture Substances 0.000 title description 23
- -1 silver halide Chemical class 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 33
- 239000000839 emulsion Substances 0.000 description 20
- 108010010803 Gelatin Proteins 0.000 description 18
- 229920000159 gelatin Polymers 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 235000019322 gelatine Nutrition 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 18
- 239000004332 silver Substances 0.000 description 18
- YLVACWCCJCZITJ-UHFFFAOYSA-N 1,4-dioxane-2,3-diol Chemical compound OC1OCCOC1O YLVACWCCJCZITJ-UHFFFAOYSA-N 0.000 description 12
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001340 alkali metals Chemical class 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 10
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 10
- 150000004679 hydroxides Chemical class 0.000 description 9
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 229910021538 borax Inorganic materials 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical group [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000837 restrainer Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HPNUYTLIFQQYCN-UHFFFAOYSA-N 4-acetylheptane-2,6-dione Chemical compound CC(=O)CC(C(C)=O)CC(C)=O HPNUYTLIFQQYCN-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004285 Potassium sulphite Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960005219 gentisic acid Drugs 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- the composition comprises a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from hydroxides and carbonates of alkali metals, 2,3- dihydroxy-l,4-dioxane (a hardener for gelatin) and a source of borate ions. It has been found that the dioxane hardener will decrease in effectiveness with age, and that such a decrease of effectiveness may be prevented or at least minimized by including in the developer borate ions. As a further feature, 1,4-diketone or diacetyl is included in the composition to enhance the hardening effect of the dioxane.
- This invention relates to photographic developing compositions and more particularly to developing compositions which are intended for the development of gelatino silver halide emulsions and contain a hardening for the gelatin.
- British Patent No. 805,120 there is claimed a method of hardening an aqueous gelatin composition which comprises incorporating therein, 2,3 dihydroxy-1,4-dioxane.
- the method of use there described is to mix the gelatin, while in the form of an aqueous solution, with a small proportion of 2,3-dihydroxy-l,4-dioxane.
- this compound will exert a useful hardening action of a gelatino silver halide emulsion if included in a developer solution employed for the development of such an emulsion.
- developer formulation which contain alkali hydroxides or carbonates
- the hardening action of the compound tends to fall off with the increasing age of the developer. It has now been found that this loss of hardening activity can be prevented or minimised by including a small proportion of borate ions in the developer.
- a photographic developer composition comprises a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydrox -l,4-dioxane and a source of borate ions.
- the developer compositions may contain additionally any of the ingredients commonly present in photographic developers, e.g. restrainers, anti-fogging agents and/or sulphites.
- the photographic developer may be any such substance known per so from the literature and includes combinations of developing substances such as those which provide a synergistic effect, e.g. a combination of metol (pmethylaminophenol) and hydroquinone.
- developing agent a combination of a 3-pyrazolidone, e.g. l-phenyl-3-pyrazolidone or analogous compounds and derivatives thereof, e.g. the 4-methyl or dimethyl derivatives together with another developer with which it affords a synergistic or so-called superadditive effect, e.g. hydroquinone, gentisic acid or ascorbic acid.
- the alkali hydroxide or carbonate may be the hydroxide or carbonate of any of the alkali metals, but is preferably a potassium or sodium compound.
- the source of borate ions is preferably borax (sodium borate), but may be boric acid or any other water-soluble salt of boric acid.
- a suitable restrainer is potassium bromide.
- Suitable anti-fogging agents are benzotriazole, 6-nitro-benzimidazole or l-phenyl-S-mercapto tetrazole and many other such compounds are known per se.
- the sulphite, when present, will usually be an alkali metal sulphite or metabisulphite, preferably the sodium or potassium salts.
- the 2,3-dihydroxy- 1,4-dioxane and the source of borate ions should preferably be present in substantially equimolar proportions.
- borax as the source of borate ions the optimum weight ration is accordingly 1 part of borax to about 0.32 part of 2,3-dihydroxy-1,4-dioxaue.
- any other soluble borate, or boric acid may be employed as the source of borate ions in equivalent amount.
- a photographic developer composition comprising a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with at least one of the following hardening agents:-diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
- the photographic developer composition comprises a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
- a 1,4-diketone which has been found useful for the invention is acetonyl acetone.
- the preferred quantities of hardening agents per litre of developing solution are 2,3-dihydroxy-1,4-dioxane 0.64 to 20 g., diacetyl l to 20 g. and 1,4-diketone 1 to 20 g.
- Example G A developer was formulated as follows:
- A 2,3-dihydroxy-l,4-dioxane 0.64-20 Borax 264
- B Diacetyl 1-20
- C Diacetonyl acetone 1-20 pH adjusted, using sodium hydroxide, to 10.0 to 10.8. Water to 1 litre.
- the film after processing in developer 8, withstood boiling water for at least /2 hour without any melting or loss of adhesion, and the swollen gelatin remained quite tough throughout. With the developer solutions containing two hardening agents loss of adhesion occurred more or less coincident with the melting point.
- a photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate 10115.
- a photographic developer composition comprising a developing agent for silver halide photographic emulsion at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxan and a source of borate ions together with a 1,4-diketone which possesses a hardening action on gelatin.
- a photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate ions, together with diacetyl.
- a photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
- a method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkali substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-l,4-dioxane and a source of borate ions.
- a method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4 dioxane a source of borate ions together with a 1,4-diketone which possesses a hardening action on gelatin.
- a method of developing and hardening a photographic silver halide emulsion having a 'developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate ions, together with diacetyl.
- a method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-l ,4 dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent 3,380,829 PHGTOGRAPHIC DEVELOPIYG *CGMPQSTEIONS Leslie Frederick Alfred Mason and Abraham Mark Sinciair, Ilford, England, assignors t0 Ilford Limited, Ilford, England, a British company No Drawing. Filed Aug. 24, 1964, Ser. No. 391,740 Claims. (Cl. 96-66) ABSTRACT OF THE DKSCLOSURE There is provided a photographic developer composition with a hardening agent for gelatin therein and method of developing and hardening the same. The composition comprises a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from hydroxides and carbonates of alkali metals, 2,3- dihydroxy-l,4-dioxane (a hardener for gelatin) and a source of borate ions. It has been found that the dioxane hardener will decrease in effectiveness with age, and that such a decrease of effectiveness may be prevented or at least minimized by including in the developer borate ions. As a further feature, 1,4-diketone or diacetyl is included in the composition to enhance the hardening effect of the dioxane.
This invention relates to photographic developing compositions and more particularly to developing compositions which are intended for the development of gelatino silver halide emulsions and contain a hardening for the gelatin.
In British Patent No. 805,120 there is claimed a method of hardening an aqueous gelatin composition which comprises incorporating therein, 2,3 dihydroxy-1,4-dioxane. The method of use there described is to mix the gelatin, while in the form of an aqueous solution, with a small proportion of 2,3-dihydroxy-l,4-dioxane.
It has been found that this compound will exert a useful hardening action of a gelatino silver halide emulsion if included in a developer solution employed for the development of such an emulsion. In the usual types of developer formulation, however, which contain alkali hydroxides or carbonates, the hardening action of the compound tends to fall off with the increasing age of the developer. It has now been found that this loss of hardening activity can be prevented or minimised by including a small proportion of borate ions in the developer. Whilst the reason for this is not known with certainty it is believed that it may be due to the formation of a complex between the 2,3-dihydroxy'1,4-dioxane and the borate of the type known to be formed between borates and compounds having vicinal hydroxy groups.
According to a first feature of the present invention, therefore, a photographic developer composition comprises a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydrox -l,4-dioxane and a source of borate ions. The developer compositions may contain additionally any of the ingredients commonly present in photographic developers, e.g. restrainers, anti-fogging agents and/or sulphites.
The photographic developer may be any such substance known per so from the literature and includes combinations of developing substances such as those which provide a synergistic effect, e.g. a combination of metol (pmethylaminophenol) and hydroquinone. Preferably, however, there is employed as developing agent a combination of a 3-pyrazolidone, e.g. l-phenyl-3-pyrazolidone or analogous compounds and derivatives thereof, e.g. the 4-methyl or dimethyl derivatives together with another developer with which it affords a synergistic or so-called superadditive effect, e.g. hydroquinone, gentisic acid or ascorbic acid.
The alkali hydroxide or carbonate may be the hydroxide or carbonate of any of the alkali metals, but is preferably a potassium or sodium compound.
The source of borate ions is preferably borax (sodium borate), but may be boric acid or any other water-soluble salt of boric acid.
A suitable restrainer is potassium bromide. Suitable anti-fogging agents are benzotriazole, 6-nitro-benzimidazole or l-phenyl-S-mercapto tetrazole and many other such compounds are known per se. The sulphite, when present, will usually be an alkali metal sulphite or metabisulphite, preferably the sodium or potassium salts.
It is found that, for optimum results the 2,3-dihydroxy- 1,4-dioxane and the source of borate ions should preferably be present in substantially equimolar proportions. Using borax as the source of borate ions the optimum weight ration is accordingly 1 part of borax to about 0.32 part of 2,3-dihydroxy-1,4-dioxaue. Instead of borax any other soluble borate, or boric acid, may be employed as the source of borate ions in equivalent amount.
It has further been found that it is possible to enhance the hardening effect of 2,3-dihydroxy-1,4-dioxane by including a proportion of other hardening agents in the developer solution.
According to another feature of the present invention there is provided a photographic developer composition comprising a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with at least one of the following hardening agents:-diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
In the preferred embodiment of the invention the photographic developer composition comprises a developing agent for a silver halide photographic emulsion, an alkali hydroxide and/or carbonate, 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
A 1,4-diketone which has been found useful for the invention is acetonyl acetone.
The preferred quantities of hardening agents per litre of developing solution are 2,3-dihydroxy-1,4-dioxane 0.64 to 20 g., diacetyl l to 20 g. and 1,4-diketone 1 to 20 g.
The following example will serve to illustrate the invention and its embodiments:
Example G. A developer was formulated as follows:
Potassium sulphite 44 Sodium sulphite 35-65 Hydroquinone l5 1-phenyl-3-pyrazolidone 0.24 Potassium bromide 8.5
Hardening agents:
(A) 2,3-dihydroxy-l,4-dioxane 0.64-20 Borax 264 (B) Diacetyl 1-20 (C) Diacetonyl acetone 1-20 pH adjusted, using sodium hydroxide, to 10.0 to 10.8. Water to 1 litre.
To illustrate the hardening effect of the various hardening agents and combinations thereof, eight developers were made up in accordance with the foregoing formulation, but subject to the variations indicated below. Each was used to develop a gelatino silver bromide photographic emulsion at F. for 1 /2 minutes, the developed materials fixed in an ammonium thiosulphate non-hardening fixing bath and washed. The melting point 3 of the gelatin in the fully processed products was determined with the following results:
Developing solution: Melting point, F.
(1) Formula as above but without hardening agents 165 (2) Above formula containing 10. ml./litre diacetyl only (B) 181 (3) Above formula containing 5.12 g./litre 2,3-dihydroxy-1,4-dioxane only (A) 183 (4) Above formula containing 6.7 nil/litre acetouyl acetone only (C) 183 (5) Above formula containing 5.12 g./litre A and ml./litre B. 191 (6) Above formula containing 10 ml./litre B and 6.7 ml./litre C. 196 (7) Above formula containing 5 .12 g./ litre A and 6.7 ml./litre C. 193
(8) Above formula containing 5.12 g./litre A, 10 ml./litre B and 6.7 ml./litre C. above 212 Norm-4n the formula for the developer whenever diacetyl is used extra sulphite must be added to allow for the fol-ma tion of the bisulphite compound.
The film, after processing in developer 8, withstood boiling water for at least /2 hour without any melting or loss of adhesion, and the swollen gelatin remained quite tough throughout. With the developer solutions containing two hardening agents loss of adhesion occurred more or less coincident with the melting point.
Considering these results it can be seen that all the hardening agents, 2,3-dihydroxy-l,4-dioxane, acetonyl acetone and diacetyl, when used alone in a developing solution not to harden the gelatin, also any combination of two such hardening agents acts to harden the gelatin to a greater extent than a single hardening agent, and when all three hardening agents are present a further increase in the hardening of the gelatin is obtained. In order to determine if this was a quantitative elTect or due to an additive action of the three hardeners, further experiments were carried out in which each of the hardening agents was used alone in the developing solution, but double the amount or" hardening agent was used, viz. 10 g./litre 2,3-dihydroxy-1,4-dioxane, ml./litre diacetyl and 13 ml./litre acetonyl acetone, but in every case no increase in the melting point of the gelatin over the figures obtained previously when the smaller quantities of hardening agent were used, was observed.
Therefore it appears that the hardening agent function differently, possibly due to each of the hardening agents preferentially cross-linking at different sites in the gelatin. Hence, to obtain the maximum hardening all three difierent hardening agents must be present in the developing solution.
We claim as our invention:
1. A photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate 10115.
2. A photographic developer according to claim 1, wherein 2,3-dihydroxy-1,4-dioxane and the source of borate ions are present in substantially equimolar proportions.
3. A photographic developer according to claim 1,'
6. A photographic developer according to claim 1, of which the pH is 10.0 to 10.8.
7. A photographic developer composition comprising a developing agent for silver halide photographic emulsion at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxan and a source of borate ions together with a 1,4-diketone which possesses a hardening action on gelatin.
8. A photographic developer composition according to claim 7, wherein the 1,4-diketone is acetonyl actone.
9. A photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate ions, together with diacetyl.
10. A photographic developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals 2,3-dihydroxy-l,4-dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
11. A photographic developer composition according to claim 10, wherein the 1,4-diketone is acetonyl acetone.
12. A method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkali substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-l,4-dioxane and a source of borate ions.
13. A method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4 dioxane a source of borate ions together with a 1,4-diketone which possesses a hardening action on gelatin.
14. A method of developing and hardening a photographic silver halide emulsion having a 'developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-1,4-dioxane and a source of borate ions, together with diacetyl.
15. A method of developing and hardening a photographic silver halide emulsion having a developable latent image which comprises treating the same with a developer composition comprising a developing agent for a silver halide photographic emulsion, at least one alkaline substance selected from the class consisting of hydroxides and carbonates of alkali metals, 2,3-dihydroxy-l ,4 dioxane and a source of borate ions, together with diacetyl and a 1,4-diketone which possesses a hardening action on gelatin.
References Cited UNITED STATES PATENTS 2,870,013 l/l959 Jeffreys 96-l.11 X 3,232,761 2/1966 Allen et al. 9666 3,232,764 2/1966 Allen et al. 9666 FOREIGN PATENTS 825,544 12/ 1959 Great Britain.
NORMAN G. TORCHIN, Primary Examiner. R. E. MARTIN, Assistant Examiner.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB13909/63A GB999145A (en) | 1963-04-08 | 1963-04-08 | Photographic developing compositions |
FR969730A FR1389922A (en) | 1963-04-08 | 1964-04-03 | Improvements to photographic developers |
GB26127/64A GB1040081A (en) | 1963-04-08 | 1964-06-24 | Photographic developing compositions |
NL6409733A NL6409733A (en) | 1963-04-08 | 1964-08-21 | |
US391740A US3380829A (en) | 1963-04-08 | 1964-08-24 | Photographic developing compositions |
CH1139264A CH445292A (en) | 1963-04-08 | 1964-09-01 | Photographic developer |
FR21937A FR88416E (en) | 1963-04-08 | 1965-06-23 | Improvements to photographic developers |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB13909/63A GB999145A (en) | 1963-04-08 | 1963-04-08 | Photographic developing compositions |
GB26127/64A GB1040081A (en) | 1963-04-08 | 1964-06-24 | Photographic developing compositions |
NL6409733A NL6409733A (en) | 1963-04-08 | 1964-08-21 | |
US391740A US3380829A (en) | 1963-04-08 | 1964-08-24 | Photographic developing compositions |
CH1139264A CH445292A (en) | 1963-04-08 | 1964-09-01 | Photographic developer |
Publications (1)
Publication Number | Publication Date |
---|---|
US3380829A true US3380829A (en) | 1968-04-30 |
Family
ID=27509422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US391740A Expired - Lifetime US3380829A (en) | 1963-04-08 | 1964-08-24 | Photographic developing compositions |
Country Status (4)
Country | Link |
---|---|
US (1) | US3380829A (en) |
CH (1) | CH445292A (en) |
GB (2) | GB999145A (en) |
NL (1) | NL6409733A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453109A (en) * | 1966-06-24 | 1969-07-01 | Eastman Kodak Co | Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position |
US5800977A (en) * | 1996-07-24 | 1998-09-01 | Eastman Kodak Company | Hardening a hydrophilic colloid composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2870013A (en) * | 1956-11-29 | 1959-01-20 | Eastman Kodak Co | Hardening of gelatin with 2,3 dihydroxy dioxane |
GB825544A (en) * | 1955-12-29 | 1959-12-16 | Kodak Ltd | Improvements in hardening gelatin |
US3232761A (en) * | 1960-03-30 | 1966-02-01 | Eastman Kodak Co | Hardening of photographic gelatin layers |
US3232764A (en) * | 1965-05-25 | 1966-02-01 | Eastman Kodak Co | Gelatin compositions adapted for the preparation of hardened coatings |
-
1963
- 1963-04-08 GB GB13909/63A patent/GB999145A/en not_active Expired
-
1964
- 1964-06-24 GB GB26127/64A patent/GB1040081A/en not_active Expired
- 1964-08-21 NL NL6409733A patent/NL6409733A/xx unknown
- 1964-08-24 US US391740A patent/US3380829A/en not_active Expired - Lifetime
- 1964-09-01 CH CH1139264A patent/CH445292A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB825544A (en) * | 1955-12-29 | 1959-12-16 | Kodak Ltd | Improvements in hardening gelatin |
US2870013A (en) * | 1956-11-29 | 1959-01-20 | Eastman Kodak Co | Hardening of gelatin with 2,3 dihydroxy dioxane |
US3232761A (en) * | 1960-03-30 | 1966-02-01 | Eastman Kodak Co | Hardening of photographic gelatin layers |
US3232764A (en) * | 1965-05-25 | 1966-02-01 | Eastman Kodak Co | Gelatin compositions adapted for the preparation of hardened coatings |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453109A (en) * | 1966-06-24 | 1969-07-01 | Eastman Kodak Co | Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position |
US5800977A (en) * | 1996-07-24 | 1998-09-01 | Eastman Kodak Company | Hardening a hydrophilic colloid composition |
Also Published As
Publication number | Publication date |
---|---|
NL6409733A (en) | 1966-02-22 |
GB999145A (en) | 1965-07-21 |
GB1040081A (en) | 1966-08-24 |
CH445292A (en) | 1967-10-15 |
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