US3125449A - Amino-phosphorylchloride hardeners - Google Patents
Amino-phosphorylchloride hardeners Download PDFInfo
- Publication number
- US3125449A US3125449A US3125449DA US3125449A US 3125449 A US3125449 A US 3125449A US 3125449D A US3125449D A US 3125449DA US 3125449 A US3125449 A US 3125449A
- Authority
- US
- United States
- Prior art keywords
- gelatin
- silver halide
- hardeners
- hardener
- light sensitive
- 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
- 239000004848 polyfunctional curative Substances 0.000 title description 20
- WDPNDMPWBDGXDB-UHFFFAOYSA-N dichloro-hydroxy-imino-$l^{5}-phosphane Chemical compound NP(Cl)(Cl)=O WDPNDMPWBDGXDB-UHFFFAOYSA-N 0.000 title 1
- 239000000839 emulsion Substances 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 19
- 239000004332 silver Substances 0.000 claims description 19
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 9
- 239000008273 gelatin Substances 0.000 description 9
- 229920000159 gelatin Polymers 0.000 description 9
- 235000019322 gelatine Nutrition 0.000 description 9
- 235000011852 gelatine desserts Nutrition 0.000 description 9
- 238000000576 coating method Methods 0.000 description 6
- -1 silver halide Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YNHXBEVSSILHPI-UHFFFAOYSA-N dimethylamidophosphoric dichloride Chemical compound CN(C)P(Cl)(Cl)=O YNHXBEVSSILHPI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LGZGDYYFARYYNC-UHFFFAOYSA-N n-difluorophosphoryl-n-methylmethanamine Chemical compound CN(C)P(F)(F)=O LGZGDYYFARYYNC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 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
- One object of my invention is to provide a hardener for gelatino silver halide photographic emulsion layers in which the photosensitive properties of the silver halides therein are not adversely affected. Other objects of my invention will appear herein.
- the compounds which have been found to be useful as gelatin hardeners have a formula (I) R NPOX (II) (R N) POX in which R is lower alkyl, e.g. methyl or ethyl and X is a halogen, particularly a chlorine, fluorine or bromine atom.
- R is lower alkyl, e.g. methyl or ethyl and X is a halogen, particularly a chlorine, fluorine or bromine atom.
- the emulsion layer containing the hardener after coating out onto a support and drying for 18 hours at 15 C. has melting points of the order of at least 100 F.
- the hardeners in accordance with my invention may be employed in gelatin-silver halide photographic emulsions to give layers or coatings which upon drying exhibit good resistance to water or aqueous conditions at elevated temperature.
- the hardening agents used in accordance with my invention are desirably employed in the proportion of 0.3-6 parts per 100 parts of gelatin.
- My invention relates to increasing the resistance of gelatin-silver halide photographic emulsions to elevated temperatures.
- the compounds used as hardeners may be either dialkylaminophosphoryldihalides, or bisdialkylaminophosphorylhalides;
- my invention is particularly useful in hardening layers of photosensitive emulsions in which high jelly strength gelatin is employed as the carrier for silver halide.
- Example 1 Samples of a fine-grain negative type sensitive gelatinsilver bromoiodide emulsion containing 67% of gelatin had incoporated therein different proportions of dimethylaminophosphoryldichloride and bisdimethylaminophosphorylchloride.
- the emulsion sample without hardener and the samples having therein the compounds referred to were each coated onto a cellulose triacetate film support and were subjected to various tests (a) 1 week after coating and (b) one week after holding at 42% RH. and
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)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
United States Patent No Drawing. Filed July 25, 1962, Ser. No. 212,465 7 Claims. (Cl. 96-111) This invention relates to light sensitive gelatino silver halide emulsions containing amino-phosphorylhalide hardeners.
Various gelatin hardeners are known for light sensitive emulsions but some of the compounds considered previously for that purpose have exhibited certain disadvantageous auxiliary characteristics which have decreased their usefulness for this purpose.
One object of my invention is to provide a hardener for gelatino silver halide photographic emulsion layers in which the photosensitive properties of the silver halides therein are not adversely affected. Other objects of my invention will appear herein.
I have found that certain amino-phosphorylhalide compounds are useful as hardeners for gelatin when incorporated in gelatino silver halide emulsions, preferably in a proportion 0.36% of the gelatin. I have found that incorporation of these compounds increases the resistance of the emulsion layer to hot water while at the same time having a low effect on contrast and some anti-fogging action. Gelatino-silver halide emulsions are characterized by the presence of gelatin in the protective colloid for the silver halide therein.
The compounds which have been found to be useful as gelatin hardeners have a formula (I) R NPOX (II) (R N) POX in which R is lower alkyl, e.g. methyl or ethyl and X is a halogen, particularly a chlorine, fluorine or bromine atom. The emulsion layer containing the hardener after coating out onto a support and drying for 18 hours at 15 C. has melting points of the order of at least 100 F. The hardeners in accordance with my invention may be employed in gelatin-silver halide photographic emulsions to give layers or coatings which upon drying exhibit good resistance to water or aqueous conditions at elevated temperature.
The hardening agents used in accordance with my invention are desirably employed in the proportion of 0.3-6 parts per 100 parts of gelatin. My invention relates to increasing the resistance of gelatin-silver halide photographic emulsions to elevated temperatures. The compounds used as hardeners may be either dialkylaminophosphoryldihalides, or bisdialkylaminophosphorylhalides; As the gelatin ordinarily for photographic purposes must have high jelly strength that is of a bloom value of at least 250 grams, my invention is particularly useful in hardening layers of photosensitive emulsions in which high jelly strength gelatin is employed as the carrier for silver halide.
The following examples illustrate my invention:
Example 1 Samples of a fine-grain negative type sensitive gelatinsilver bromoiodide emulsion containing 67% of gelatin had incoporated therein different proportions of dimethylaminophosphoryldichloride and bisdimethylaminophosphorylchloride. The emulsion sample without hardener and the samples having therein the compounds referred to were each coated onto a cellulose triacetate film support and were subjected to various tests (a) 1 week after coating and (b) one week after holding at 42% RH. and
3,125,449 Patented Mar. 17, 1964 "ice F. such as for speed, fog, contrast, and melting point, the latter determined when the emulsion is immersed in water and the temperature is increased from room temperature up to the boiling point of the water. The results obtained with the chlorides were as follows:
1 week after coating 1 week at 42% R.H. and 120 F.
Control 4. 30 24 89 94 Control Compound (I; R=Me) 0.3 g./l.) 4. 32 21 86 103 Control Compound (I; R=Me) (1.0 g. l 4. 24 16 87 180 Control Compound (II; R=Me) (0.3 g./ 4. 33 19 85 Control Compound (II; R=Me) The product, after it had been coated for 3 months, was run through the same series of tests and the following results were obtained:
Samples of the film after standing for 6 months were run through this series of tests and the following results were obtained:
6 months after coating Rel. Fog Con- M.P. Speed trast F.)
Control 4. 30 0. l9 0. 94 92 Control Compound (I; R=Me) (1.0 g./l.) 4.21 0.13 0.88 198 Control Compound (II; R=Me) Example 2 The above example was repeated except that the corresponding fluoride compounds (dimethylaminophosphoryldifluoride and bisdimethylphosphorylfluoride) were employed in place of the chlorides used in Example 1, the quantities being unchanged. The fluorides gave characteristics substantially equivalent to those imparted by the chlorides in the photographic emulsions of Example 1.
Example 3 Hardeners were used having the following formulas:
(IV) Et NPOCI (V) (Et N) POCl and (VI) (Et N) POF These hardeners were incorporated in a gelatin-silver halide photographic emulsion and coated out in the form of layers thereon. Tests were run on the layers as indicated in the following tables and the results which were obtained were those given comparing the speed, fog, contrast, and melting points of the different layers:
1 week after coating Rel. Fog Con- M.1
Speed trast F) Control 4. 37 .20 98 91 Control Compound (IV) (1.0 g 4. 31 .16 .98 95 Control Compound (IV)(3.0 g 4. 21 12 .98 100 Control Compound (V) (1.0 g. 4. 32 .17 1. 96
1 week at 42% RH. and 120 F.
Compound (VI) bi'sdiethylaminophosphorylfluoride as a hardener acted similarly to the corresponding chloride in the gelatin-silver halide emulsion.
I claim:
1. A light sensitive gelatin-silver halide photographic emulsion containing a hardener selected from the group consisting of R NPOX and (R N) POX, R being lower alkyl and X being halide.
2. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein R NPOCI R being lower alkyl.
3. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein (R N) POCl, R being lower alkyl.
4. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein (R N) POF, R being lower alkyl.
5. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein Et NPOCI Et representing ethyl.
6. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein (Et N) POCl, Et representing ethyl.
7. A light sensitive gelatin-silver halide photographic emulsion containing as a hardener therein (Et N) POF. Et representing ethyl.
No references cited.
Claims (1)
1. A LIGHT SENSITIVE GELATIN-SILVER HALIDE PHOTOGRAPHIC EMULSION CONTAINING A HARDER SELECTED FROM THE GROUP CONSISTING OF R2NPOX2 AND (R2N)2POX, R BEING LOWER ALKYL AND X BEING HALIDE.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21246562A | 1962-07-25 | 1962-07-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3125449A true US3125449A (en) | 1964-03-17 |
Family
ID=22791140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3125449D Expired - Lifetime US3125449A (en) | 1962-07-25 | Amino-phosphorylchloride hardeners |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3125449A (en) |
| GB (2) | GB974723A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668616A (en) * | 1984-11-28 | 1987-05-26 | Fuji Photo Film Co., Ltd. | Process for hardening gelatin |
| US5073480A (en) * | 1989-07-14 | 1991-12-17 | Agfa-Gevaert, N.V. | Quick acting hardener for photographic gelatin layers |
| WO2008038764A1 (en) | 2006-09-28 | 2008-04-03 | Fujifilm Corporation | Spontaneous emission display, spontaneous emission display manufacturing method, transparent conductive film, electroluminescence device, solar cell transparent electrode, and electronic paper transparent electrode |
| EP2385425A1 (en) | 2010-05-07 | 2011-11-09 | Fujifilm Corporation | Silver halide photographic light-sensitive material for movie |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59188641A (en) | 1983-04-11 | 1984-10-26 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion |
| US6468339B1 (en) | 2001-08-23 | 2002-10-22 | Eastman Kodak Company | Alumina filled gelatin |
| EP2619628B1 (en) | 2010-09-17 | 2014-03-26 | Fujifilm Manufacturing Europe BV | Photographic paper and its use in a photo album |
| GB202006061D0 (en) | 2020-04-24 | 2020-06-10 | Fujifilm Mfg Europe Bv | Photographic paper |
-
0
- US US3125449D patent/US3125449A/en not_active Expired - Lifetime
-
1963
- 1963-07-25 GB GB29442/63A patent/GB974723A/en not_active Expired
-
1964
- 1964-01-21 GB GB2593/64A patent/GB1004658A/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668616A (en) * | 1984-11-28 | 1987-05-26 | Fuji Photo Film Co., Ltd. | Process for hardening gelatin |
| US5073480A (en) * | 1989-07-14 | 1991-12-17 | Agfa-Gevaert, N.V. | Quick acting hardener for photographic gelatin layers |
| WO2008038764A1 (en) | 2006-09-28 | 2008-04-03 | Fujifilm Corporation | Spontaneous emission display, spontaneous emission display manufacturing method, transparent conductive film, electroluminescence device, solar cell transparent electrode, and electronic paper transparent electrode |
| EP2385425A1 (en) | 2010-05-07 | 2011-11-09 | Fujifilm Corporation | Silver halide photographic light-sensitive material for movie |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1004658A (en) | 1965-09-15 |
| GB974723A (en) | 1964-11-11 |
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