US3676144A - Epoxide hardener in silver halide emulsion layer and formaldehyde and/or glyoxal hardener in adjacent protective layer - Google Patents
Epoxide hardener in silver halide emulsion layer and formaldehyde and/or glyoxal hardener in adjacent protective layer Download PDFInfo
- Publication number
- US3676144A US3676144A US42865A US3676144DA US3676144A US 3676144 A US3676144 A US 3676144A US 42865 A US42865 A US 42865A US 3676144D A US3676144D A US 3676144DA US 3676144 A US3676144 A US 3676144A
- Authority
- US
- United States
- Prior art keywords
- hardener
- formaldehyde
- glyoxal
- layer
- silver halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 34
- 239000000839 emulsion Substances 0.000 title abstract description 20
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 title abstract description 20
- -1 silver halide Chemical class 0.000 title abstract description 12
- 229940015043 glyoxal Drugs 0.000 title abstract description 10
- 229910052709 silver Inorganic materials 0.000 title abstract description 6
- 239000004332 silver Substances 0.000 title abstract description 6
- 239000010410 layer Substances 0.000 title description 19
- 239000011241 protective layer Substances 0.000 title description 7
- 239000004848 polyfunctional curative Substances 0.000 title description 6
- 150000002118 epoxides Chemical class 0.000 title 1
- 108010010803 Gelatin Proteins 0.000 abstract description 13
- 229920000159 gelatin Polymers 0.000 abstract description 13
- 235000019322 gelatine Nutrition 0.000 abstract description 13
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 13
- 239000008273 gelatin Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000008961 swelling Effects 0.000 description 9
- 150000002924 oxiranes Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/30—Hardeners
Definitions
- the present invention relates to a light-sensitive photographic material with reduced swelling.
- binding agents may consist of gelatin, vinyl polymers, cellulose derivatives, and casein, among others, or mixtures thereof. All these materials have in common that they more or less swell in the presence of water, becoming permeable for dissolved particles and thus as a photographic layer make possible the developing process.
- the swelling of these layers is necessary on the one hand for the processability but is disadvantageous on the other hand due to the mechanical vulnerability of the expanded layers. For this reason, photographic materials are hardened in order to give them sufficient mechanical strength. High-speed processing of sheet film places particularly high demands on the mechanical stability of the expanded material. In addition, short drying times are required, which result only from a correspondingly decreased layer swelling.
- the hardening agents employed previously for this purpose were mainly Formalin, oxyaldehyde, dialdehyde, such as glyoxal and homologs, polymeric dialdehydes, chlorinated aldehyde acids, such as mucochloric acid and mucobromic acid, among others, polyfunctional acid chloride, activated silver halide compounds, chromium salts, divinyl sulfone, carbodiimide and diepoxide. All these hardening agents have in common that they react with functional groups of the gelatin side chains and effect thereby cross-linking which result in a raising of the fusion point, a decrease of the expansion and consequently a diminished vulnerability of the layer in the expanded state.
- hardening agents described in the literature relatively only a few have reached practical importance. This applies to the secondary requirements which are placed on good hardening agents aside from their crosslinking property, such as for example no damaging effect on the sensitometric properties of the emulsion, the highest possible hardening speed, non-toxicity, moderate volatility or none at all, strong reduction in the capacity to swell of the gelatins, no disadvantageous influence of the UV transmittancy of the hardened layer and no viscosity rise during storage time of the emulsion ready for pouring.
- the object of the present invention was to synthesize a mechanically stable, as little as possible swelling layer without having to accept losses worth mentioning in sensitivity and gradation.
- the UV transmittal should not be encroached upon and one should be able to apply the layer with high speed, i.e. in very concentrated form.
- this is achieved by the combination of a hardening with formaldehyde and/or glyoxal over the protective layer and an epoxide hardening in the emulsion with compounds having at least two epoxide radicals which are obtained by the conversion of epichlorhydrin or epihydrinic alcohol with compounds containing amino, hydroxyl, carboxyl or sulfo groups or their functional derivatives, such as anhydrides, acid chlorides or betaines.
- a further essential advantage of layers hardened in such a manner is their very good transmittal for UV light in the range of 300-400 me, which in the further processes of the photographic material, e.g. in copying processes, is of importance.
- the particular advantage of the invention is that an optimum hardening effect is obtained when the hardening agents are distributed between two layers, and in particular the epoxide in the emulsion and Formalin and/ or glyoxal in the protective layer. Lesser expansion quotients are thus obtained with the same molar amounts.
- the above-described emulsions in addition to the hardening agents, may contain in a customary manner still further additives, such as optical and chemical sensitizers, coating auxiliary agents, and others.
- the novel protective layer besides the hardening agents formaldehyde and glyoxal, may contain the customary binding agents, synthetic materials, delustering agents, coating auxiliary agents, filter dyes, and others.
- EXAMPLE 1 A silver iodine bromide emulsion of medium sensitivity, ready for pouring, with 90 g. gelatin and ca. 60 g. AgNO per liter is divided into equal samples and to these are added the below-given amounts of epoxy compounds. These emulsions were subsequently poured on the base with a coating of 7.7 g. gelatin and 9.6 g. AgNO /m. Over that was drawn a protective gelatin layer which in addition to the necessary coating auxiliary agents contained 300 mg. formaldehyde as the hardening agent. After drying, the samples were stored at 22 C. and ca. 45% relative humidity and all samples were checked for their hardening condition after one week and after two months storage.
- Example 2 To an emulsion according to Example 1 are added increasing amounts of the compound 4. Subsequently there occur a coating and an overlay with a protective layer, which per liter of solution contains 15 g. gelatin, wetting agent, SiO for roughening the surface, preserving agent as well as 200 mg. formaldehyde and 400 mg. glyoxal.
- a protective layer which per liter of solution contains 15 g. gelatin, wetting agent, SiO for roughening the surface, preserving agent as well as 200 mg. formaldehyde and 400 mg. glyoxal.
- the data obtained after the pouring and corresponding storage are given in the following table.
- EXAMPLE 3 To an emulsion according to Example 1 are added the below-stated amounts of hardening agents, the mixture 4 is poured, and subsequently is coated with a protective layer according to Example 1. Particulars and results are given in the following table.
- a light-sensitive material comprising at least one light-sensitive silver halide emulsion layer having decreased expansion and improved UV transmittancy properties, which contains an epoxide hardener compound selected from those having the formula:
- R being a short chain alkyl group
- R being a short chain alkyl group with 2 to 5 C
- the light-sensitive material also having a protective gelatin layer contiguous with said silver halide emulsion layer and containing a hardener selected from the group consisting of formaldehyde and glyoxal in a molar ratio to the epoxide hardener of from 5:1 to 1:5.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691928356 DE1928356A1 (de) | 1969-06-04 | 1969-06-04 | Photographische Halogensilberemulsion mit verminderter Quellung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3676144A true US3676144A (en) | 1972-07-11 |
Family
ID=5736029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US42865A Expired - Lifetime US3676144A (en) | 1969-06-04 | 1970-06-02 | Epoxide hardener in silver halide emulsion layer and formaldehyde and/or glyoxal hardener in adjacent protective layer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3676144A (enrdf_load_stackoverflow) |
| BE (1) | BE751134A (enrdf_load_stackoverflow) |
| DE (1) | DE1928356A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2049930A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1251609A (enrdf_load_stackoverflow) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5091315A (enrdf_load_stackoverflow) * | 1973-12-13 | 1975-07-22 | ||
| JPS5096216A (enrdf_load_stackoverflow) * | 1973-12-24 | 1975-07-31 | ||
| US3989529A (en) * | 1974-10-29 | 1976-11-02 | Gaf Corporation | Hydrophilic coupler solutions |
| US4399214A (en) * | 1977-12-30 | 1983-08-16 | Agfa-Gevaert Aktiengesellschaft | Process for hardening color photographic silver halide emulsion layers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3670701D1 (de) * | 1986-09-23 | 1990-05-31 | Agfa Gevaert Nv | Dextranderivate enthaltende, photographische oberflaechenschichten. |
-
1969
- 1969-06-04 DE DE19691928356 patent/DE1928356A1/de active Pending
-
1970
- 1970-05-29 BE BE751134D patent/BE751134A/nl unknown
- 1970-06-02 GB GB1251609D patent/GB1251609A/en not_active Expired
- 1970-06-02 US US42865A patent/US3676144A/en not_active Expired - Lifetime
- 1970-06-04 FR FR7020574A patent/FR2049930A5/fr not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5091315A (enrdf_load_stackoverflow) * | 1973-12-13 | 1975-07-22 | ||
| JPS5096216A (enrdf_load_stackoverflow) * | 1973-12-24 | 1975-07-31 | ||
| US3989529A (en) * | 1974-10-29 | 1976-11-02 | Gaf Corporation | Hydrophilic coupler solutions |
| US4399214A (en) * | 1977-12-30 | 1983-08-16 | Agfa-Gevaert Aktiengesellschaft | Process for hardening color photographic silver halide emulsion layers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1928356A1 (de) | 1970-12-10 |
| FR2049930A5 (enrdf_load_stackoverflow) | 1971-03-26 |
| GB1251609A (enrdf_load_stackoverflow) | 1971-10-27 |
| BE751134A (nl) | 1970-11-30 |
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