US1941852A - Photographic gelatin layer - Google Patents
Photographic gelatin layer Download PDFInfo
- Publication number
- US1941852A US1941852A US656196A US65619633A US1941852A US 1941852 A US1941852 A US 1941852A US 656196 A US656196 A US 656196A US 65619633 A US65619633 A US 65619633A US 1941852 A US1941852 A US 1941852A
- Authority
- US
- United States
- Prior art keywords
- gelatin
- hardening
- photographic
- gelatin layer
- grams
- 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
- 108010010803 Gelatin Proteins 0.000 title description 25
- 229920000159 gelatin Polymers 0.000 title description 25
- 239000008273 gelatin Substances 0.000 title description 25
- 235000019322 gelatine Nutrition 0.000 title description 25
- 235000011852 gelatine desserts Nutrition 0.000 title description 25
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class 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 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- AEQIWNAVOHVCNG-UHFFFAOYSA-N sodium;1,2-dihydroxyethane-1,2-disulfonic acid Chemical compound [Na+].OS(=O)(=O)C(O)C(O)S(O)(=O)=O AEQIWNAVOHVCNG-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 241001479434 Agfa Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- -1 bisulfite compound Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance 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
- G03C1/301—Aldehydes or derivatives thereof, e.g. bisulfite addition products
Definitions
- derivatives of the dialdehydes are very well suited for hardening photographic gelatin layers. These derivatives have at least one of their aldehyde groups substituted so as to correspond with 5 the following general formula wherein X represents hydrogen or the radical of an inorganic acid or an organic acid and Y represents the acid radical ofan inorganic acid or an organic acid. If X represents H and Y SOzNa there results the bisulfite compound of the alde-f hyde. If X and Y represent, for instance, Cl-IaIJO there results the tetra-acetate of the dialdehvde.
- the hardening action of the dialdehydederivatives becomes more intense with an increasing pH value of the gelatin used.
- the hardening of photographic materials takes place in twostages.
- a first hardening efiect occurs after incorporating the hardening agent in the gelatin and, because in this stage there still remains undecomposed derivative a second hardening occurs in developing the exposed photographic material.
- This hardening in two stages has the advantage that they developer more easily penetrates 'the photographic layer though substantially the same hardening effect may be finally obtained as with the free dialdehydes. This is evidenced by thefollowing experiment.
- The'protographic layers hardened with the aldehyde derivatives I disclosed show a good stability. Moreover, the aldehyde derivatives form solid substances and are more stable and easier to handle than are liquid aldehydes.
- the quantity of dialdehyde derivative added to the gelatin amounts to about 0.2 to 5 grams per 100 grams of gelatin, however, my invention is not limited to this range given rather for illustration. The most suitable amount can be easily determined by experiment. If too large quantities of hardening agent are added to the gelatin, the same may crystallize out and thus impair the finished layer.
- the addition of the hardening agent is made in form of. a solution preferably an aqueous solution. If the compoundis insoluble in water any solvent may be used which is sufficiently miscible with water, for instance, alcohol, methanol and acetone.
- the addition 80 is preferably made to the finished gelatin solution before being cast.
- Example 1500 grams of a gelatino-silver- 8 halide emulsion containing about 90 to 100 grams of gelatin are mixed with 5 cc. of an aqueous solution of 10 per cent strength of glyoxal-sodiumbisulfite. Then the mixture is cast onto a support of glass or a film and dried. The layer obtained melts at 34 0., whereas the unhardened emulsion melts at 31 C.
- Example 2500 grams of a gelatinovsilverhalide emulsion containing about 90 to 100 grams of gelatin are 'mixed with 15 cc. of an alcoholic solution of 2 percent strength of glyoxal-tetraacetate and then cast. After drying the emulsion has a melting point0f 33 (3., whereas the unhardened emulsion melts at 31 C.
- a photographic material provided with a gelatin layer containing besides the condensation product of gelatin with a dialdehyde, a substantial amount of aderivative of the dialdehyde, at least one of the aldehyde groups being substituted, so as to correspond with the formula.
- a photographic material provided with a gelatin layer containing the condensation product of gelatin with glyoxal besides a substantial amount of glyoxal-sodiumbisulfite.
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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
irso STATES rATsNT o i-icEj rno'roGnArnIc GELATIN LAYER Johannes Brunken, Dessau in Anhalt, Germany,
v assignor to Agfa Ansco Corporation, Binghamton, N. Y., a corporation of New York 'No' Drawing.
Application February 10, 1933,
Serial No. 656,196, and in Germany February 4 Claims. (Cl. 95-7) My present invention relates to hardening of photographic gelatin layers.
One of its objects is a hardened photographic gelatin layer. Further objects'will be seen from the detailed specification following hereafter.
In my application Ser. No. 549,331 matured into Patent 1,870,354, I have described photographic gelatin layers hardened by means of dialdehydes.
According to this invention I have found that derivatives of the dialdehydes are very well suited for hardening photographic gelatin layers. These derivatives have at least one of their aldehyde groups substituted so as to correspond with 5 the following general formula wherein X represents hydrogen or the radical of an inorganic acid or an organic acid and Y represents the acid radical ofan inorganic acid or an organic acid. If X represents H and Y SOzNa there results the bisulfite compound of the alde-f hyde. If X and Y represent, for instance, Cl-IaIJO there results the tetra-acetate of the dialdehvde.
The hardening action of my new hardening agents is probably caused by the separation of free aldehyde from the derivatives enumerated. This is evidenced by the fact that the gelatin used must have a minimum pH value which is generally about pH=4 (gelatin as usually on the market has a value of pH=5 to 8) whenmeasured after the method disclosed by Tiidt in Chemikerzeitung 1927, pages 302 to 303. As the dialdehyde derivatives included in my invention can be easily saponified, gelatin of the value of pH=4 appears to be sufiicient to saponify part of the aldehyde derivative added which effects the hardening. The hardening action of the dialdehydederivatives becomes more intense with an increasing pH value of the gelatin used.
The hardening of photographic materials takes place in twostages. A first hardening efiect occurs after incorporating the hardening agent in the gelatin and, because in this stage there still remains undecomposed derivative a second hardening occurs in developing the exposed photographic material. This hardening in two stages has the advantage that they developer more easily penetrates 'the photographic layer though substantially the same hardening effect may be finally obtained as with the free dialdehydes. This is evidenced by thefollowing experiment.
When testing gelatin having incorporated glyoxal-sodiumbisulfite in water it will melt at 34 C. and when testing the same gelatin in a developer (containing 40 grams of potassium carbonate and 40 grams of sodium sulfite perliter) it will melt at 43 C.
The'protographic layers hardened with the aldehyde derivatives I disclosed show a good stability. Moreover, the aldehyde derivatives form solid substances and are more stable and easier to handle than are liquid aldehydes. The quantity of dialdehyde derivative added to the gelatin amounts to about 0.2 to 5 grams per 100 grams of gelatin, however, my invention is not limited to this range given rather for illustration. The most suitable amount can be easily determined by experiment. If too large quantities of hardening agent are added to the gelatin, the same may crystallize out and thus impair the finished layer. The addition of the hardening agent is made in form of. a solution preferably an aqueous solution. If the compoundis insoluble in water any solvent may be used which is sufficiently miscible with water, for instance, alcohol, methanol and acetone. The addition 80 is preferably made to the finished gelatin solution before being cast.
The following examples illustrate the invention:
Example 1.500 grams of a gelatino-silver- 8 halide emulsion containing about 90 to 100 grams of gelatin are mixed with 5 cc. of an aqueous solution of 10 per cent strength of glyoxal-sodiumbisulfite. Then the mixture is cast onto a support of glass or a film and dried. The layer obtained melts at 34 0., whereas the unhardened emulsion melts at 31 C.
Example 2.500 grams of a gelatinovsilverhalide emulsion containing about 90 to 100 grams of gelatin are 'mixed with 15 cc. of an alcoholic solution of 2 percent strength of glyoxal-tetraacetate and then cast. After drying the emulsion has a melting point0f 33 (3., whereas the unhardened emulsion melts at 31 C.
The invention is not limited to the foregoing examples nor to the specific details given therein. Other dialdehyde derivatives of the kind set forth herein may be used without departing from the scope of my invention.
What I claim is:
1. A photographic material provided with a gelatin layer containing besides the condensation product of gelatin with a dialdehyde, a substantial amount of aderivative of the dialdehyde, at least one of the aldehyde groups being substituted, so as to correspond with the formula.
OH- Y0 wherein X represents hydrogen or the radical of an organic or inorganic acid and Y represents the acid radical of an organic or inorganic acid. 3. A photographic material provided with a gelatin layer containing the condensation product of gelatin with glyoxal besides a substantial amount of glyoxal-sodiumbisulfite.
4.'A photographic material provided with a gelatin layer containing the condensation product of gelatin with glyoxal besides a substantial amount of glyoxal-tetra-acetate.
' J OHANNES BRUNKEN.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI43763D DE585920C (en) | 1932-02-16 | 1932-02-16 | Process for hardening photographic layers, in particular photographic gelatin layers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1941852A true US1941852A (en) | 1934-01-02 |
Family
ID=6422248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US656196A Expired - Lifetime US1941852A (en) | 1932-02-16 | 1933-02-10 | Photographic gelatin layer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US1941852A (en) |
| BE (1) | BE394394A (en) |
| DE (1) | DE585920C (en) |
| FR (1) | FR43111E (en) |
| GB (1) | GB408085A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2663639A (en) * | 1950-01-28 | 1953-12-22 | Harris Seybold Co | Printing plate preparation |
| US3103437A (en) * | 1959-04-10 | 1963-09-10 | Hardening | |
| US3212895A (en) * | 1960-12-20 | 1965-10-19 | Eastman Kodak Co | Stability of rapid-processed photographic materials |
-
0
- BE BE394394D patent/BE394394A/xx unknown
-
1932
- 1932-02-16 DE DEI43763D patent/DE585920C/en not_active Expired
-
1933
- 1933-02-10 US US656196A patent/US1941852A/en not_active Expired - Lifetime
- 1933-02-16 GB GB4788/33A patent/GB408085A/en not_active Expired
- 1933-02-16 FR FR43111D patent/FR43111E/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2663639A (en) * | 1950-01-28 | 1953-12-22 | Harris Seybold Co | Printing plate preparation |
| US3103437A (en) * | 1959-04-10 | 1963-09-10 | Hardening | |
| US3212895A (en) * | 1960-12-20 | 1965-10-19 | Eastman Kodak Co | Stability of rapid-processed photographic materials |
Also Published As
| Publication number | Publication date |
|---|---|
| BE394394A (en) | |
| DE585920C (en) | 1933-10-12 |
| GB408085A (en) | 1934-04-05 |
| FR43111E (en) | 1934-02-12 |
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