US2865753A - Photographic emulsions containing a styrene-butadiene latex and photographic paper made therewith - Google Patents
Photographic emulsions containing a styrene-butadiene latex and photographic paper made therewith Download PDFInfo
- Publication number
- US2865753A US2865753A US552989A US55298955A US2865753A US 2865753 A US2865753 A US 2865753A US 552989 A US552989 A US 552989A US 55298955 A US55298955 A US 55298955A US 2865753 A US2865753 A US 2865753A
- Authority
- US
- United States
- Prior art keywords
- photographic
- styrene
- emulsion
- paper
- butadiene
- 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
- 239000000839 emulsion Substances 0.000 title claims description 40
- 239000004816 latex Substances 0.000 title claims description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims description 15
- 239000002174 Styrene-butadiene Substances 0.000 title claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims description 12
- 239000011115 styrene butadiene Substances 0.000 title claims description 12
- 229920000126 latex Polymers 0.000 title description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000001143 conditioned effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGDLSKPZMOTRTR-OAPYJULQSA-N (4z)-4-heptadecylidene-3-hexadecyloxetan-2-one Chemical compound CCCCCCCCCCCCCCCC\C=C1/OC(=O)C1CCCCCCCCCCCCCCCC NGDLSKPZMOTRTR-OAPYJULQSA-N 0.000 description 1
- OILSMOCIMSQVCU-UHFFFAOYSA-N 2-hexadecylicos-1-ene-1,3-dione Chemical compound CCCCCCCCCCCCCCCCCC(=O)C(=C=O)CCCCCCCCCCCCCCCC OILSMOCIMSQVCU-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- -1 silver halide Chemical class 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- This invention relates to photographic emulsions in which styrene-butadiene polymer has been incorporated and to photographic papers in which those emulsions have been employed as the sensitizing layer.
- paper base is employed in the making of some photographic products in which the paper has been treated with a resin to translucentize the paper or with a resin latex to impart waterresistant properties thereto.
- paper has been employed which has been melt coated with a resin such as polymethyl styrene or with a cellulose derivative such as cellulose acetate butyrate.
- silver halide emulsion layers are poorly adhesive to the support, often necessitating intermediate layers.
- photographic papers are manufactured at high rates of production which necessitates fast drying of the emulsion layer after its having been applied to the paper.
- the rapid drying of a photographic emulsion layer may cause brittleness and in the high-speed production of photographic paper this brittleness may become a serious problem.
- One object of our invention is to provide photographic emulsions which exhibit good adherence to resin-treated paper base. Another object of our invention is to reduce the brittleness characteristics of photographic emulsion layers. A further object of our invention is to provide a photographic paper, the base of which is resistant to the eifects of water, or is translucent, characterized by adherence of the emulsion layer to the entire paper base and with freedom from frilling. A further object of our invention is to provide photographic emulsions containing styrene-butadiene polymer therein. Other objects of our invention will appear herein.
- the elastomer is preferably supplied to the photographic emulsion in the form of its primary aqueous emulsion such as an aqueous dispersion or latex in which the latex is formed by the emulsion copolymerization of styrene and butadiene.
- Styrene-butadiene polymers in latex form are well known in the art having been mentioned in various disclosures such as in U. S. Patents Nos. 2,537,114; 2,685,538; and 2,685,571.
- Example 2 Styrene-butadiene resin in the form of its primary aqueous dispersion was added to a gelatin-silver halide photographic emulsion in the proportion of 33% solid weight based on the gelatin in the photographic emulsion.
- the emulsion so prepared was applied to a paper base which had been sized with Aquapel 380 (stearoyl hexadecyl ethenone). It was found that good bonding was effected between the photographic emulsion applied to the Aquapel-sized paper and the paper itself.
- Aquapel 380 stearoyl hexadecyl ethenone
- Example 3 To two samples of a gelatin-silver halide photographic emulsion was added just before coating a Water dispersion or latex of a 60:40 styrene-butadiene copolymer of 48% solids concentration in proportions of 25% and of 50% of the gelatin present.
- the latex employed is known in the trade as Dow 512K. These emulsions were coated on waterproofed paper. The paper was dried and conditioned at 18% relative humidity at F. for 15 hours together with paper coated and dried under the same conditions but latex had not been added to the emulsion. Strips of the paper were drawn with tension over a /2 inch cylinder. The paper coated with emulsion contained 25% and 50% of the latex, showed 16 and 5 cracks per inch respectively whereas the paper coated with emulsion which did not contain latex showed cracking of 34 cracks to the inch.
- Example 4 A 60:40 styrene-butadiene latex having a 40% solids content prepared by an emulsion polymerization was added to a photographic emulsion in the proportion of 18% of styrene-butadiene resin based on the weight of the gelatin in the emulsion. Paper base was coated therewith and the paper thus prepared was exposed, processed, ferrotyped, and conditioned as described in Example 3, along with a paper prepared from emulsion to which no latex was added. The conditioned paper was put through a series of small flexing rolls known as a Morse Print Straightener. The latex-containing sample was rated as good for print straightener cracks; the comparison was bad.
- composition of matter comprising a gelatin-silver halide photographic emulsion in which has been incorporated a styrene-butadiene latex resulting from the emulsion polymerization of styrene and butadiene in the pro- 3 portions of 55-65% of the former and 45-35% of the latter.
- a method of preparing photographic papers which comprises incorporating in a gelatin-silver halide photographic emulsion a minor proportion of styrene-butadiene latex and coating the paper with a layer of the emulsion.
- a method of preparing photographic paper which comprises adding to a gelatin-silver halide photographic emulsion a styrene-butadiene elastomer prepared by polymerizing together styrene and butadiene in an emulsion polymerization in which styrene constitutes 5565% and butadiene 45-35% of their mixture, and applying a layer of the emulsion to a paper base.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Kearney P. Gritfin and William H. Griggs, Rochester,
N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey g No Drawing. Application December f4, 1955 Serial No. 552,989
4 Claims. (Cl. 96-114) This invention relates to photographic emulsions in which styrene-butadiene polymer has been incorporated and to photographic papers in which those emulsions have been employed as the sensitizing layer.
In various types of photographic papers special paper base is employed to impart particular characteristics to the product obtained. For instance, paper base is employed in the making of some photographic products in which the paper has been treated with a resin to translucentize the paper or with a resin latex to impart waterresistant properties thereto. In some cases paper has been employed which has been melt coated with a resin such as polymethyl styrene or with a cellulose derivative such as cellulose acetate butyrate. In those cases, silver halide emulsion layers are poorly adhesive to the support, often necessitating intermediate layers.
Sometimes photographic papers are manufactured at high rates of production which necessitates fast drying of the emulsion layer after its having been applied to the paper. The rapid drying of a photographic emulsion layer may cause brittleness and in the high-speed production of photographic paper this brittleness may become a serious problem.
One object of our invention is to provide photographic emulsions which exhibit good adherence to resin-treated paper base. Another object of our invention is to reduce the brittleness characteristics of photographic emulsion layers. A further object of our invention is to provide a photographic paper, the base of which is resistant to the eifects of water, or is translucent, characterized by adherence of the emulsion layer to the entire paper base and with freedom from frilling. A further object of our invention is to provide photographic emulsions containing styrene-butadiene polymer therein. Other objects of our invention will appear herein.
We have found that by incorporating styrene-butadiene elastomer in gelatin-silver halide photographic emulsions the emulsions so prepared exhibit good adherence to paper particularly paper which has been resin treated. We have found that by incorporating sytrene-butadiene elastomers in photographic emulsions the emulsion layers of photographic papers prepared thereby exhibit flexibility properties even after they have been subjected to fast drying in the manufacture of the photographic paper. The elastomers which we employ are prepared by polymerizing together styrene and butadiene in the proportions of 55-65% of the former and 45*35% of the latter. The elastomer is preferably supplied to the photographic emulsion in the form of its primary aqueous emulsion such as an aqueous dispersion or latex in which the latex is formed by the emulsion copolymerization of styrene and butadiene. Styrene-butadiene polymers in latex form are well known in the art having been mentioned in various disclosures such as in U. S. Patents Nos. 2,537,114; 2,685,538; and 2,685,571.
The following examples are illustrative of our invention: I
! nitecl States Patent r 2,865,753 r Patented Dec. 23, 1958 Example 1 To samples of a gelatin-silver halide photographic emulsion of the negative type was added styrene-butadiene latex in amounts varying from 12.5 to 50% solid weight based on the weight of the gelatin in the emulsion. These samples were coated on -a resin-treated paper base. The sensitized papers thus obtained were exposed and developed photographically. Good photographic images were obtained and the unexposed portions were free from fog. The preparation of the emulsion and its processing were carried out under darkened conditions.
Example 2 Styrene-butadiene resin in the form of its primary aqueous dispersion was added to a gelatin-silver halide photographic emulsion in the proportion of 33% solid weight based on the gelatin in the photographic emulsion. The emulsion so prepared was applied to a paper base which had been sized with Aquapel 380 (stearoyl hexadecyl ethenone). It was found that good bonding was effected between the photographic emulsion applied to the Aquapel-sized paper and the paper itself.
Example 3 To two samples of a gelatin-silver halide photographic emulsion was added just before coating a Water dispersion or latex of a 60:40 styrene-butadiene copolymer of 48% solids concentration in proportions of 25% and of 50% of the gelatin present. The latex employed is known in the trade as Dow 512K. These emulsions were coated on waterproofed paper. The paper was dried and conditioned at 18% relative humidity at F. for 15 hours together with paper coated and dried under the same conditions but latex had not been added to the emulsion. Strips of the paper were drawn with tension over a /2 inch cylinder. The paper coated with emulsion contained 25% and 50% of the latex, showed 16 and 5 cracks per inch respectively whereas the paper coated with emulsion which did not contain latex showed cracking of 34 cracks to the inch.
Example 4 Example 5 A 60:40 styrene-butadiene latex having a 40% solids content prepared by an emulsion polymerization was added to a photographic emulsion in the proportion of 18% of styrene-butadiene resin based on the weight of the gelatin in the emulsion. Paper base was coated therewith and the paper thus prepared was exposed, processed, ferrotyped, and conditioned as described in Example 3, along with a paper prepared from emulsion to which no latex was added. The conditioned paper was put through a series of small flexing rolls known as a Morse Print Straightener. The latex-containing sample was rated as good for print straightener cracks; the comparison was bad.
We claim:
1. A composition of matter comprising a gelatin-silver halide photographic emulsion in which has been incorporated a styrene-butadiene latex resulting from the emulsion polymerization of styrene and butadiene in the pro- 3 portions of 55-65% of the former and 45-35% of the latter.
2. A gelatin-silver halide photographic emulsion containing therein a styrene-butadiene latex in an amount of 12.550% solid Weight based onthe weight of the gelatin in the emulsion.
3. A method of preparing photographic papers which comprises incorporating in a gelatin-silver halide photographic emulsion a minor proportion of styrene-butadiene latex and coating the paper with a layer of the emulsion.
4. A method of preparing photographic paper which comprises adding to a gelatin-silver halide photographic emulsion a styrene-butadiene elastomer prepared by polymerizing together styrene and butadiene in an emulsion polymerization in which styrene constitutes 5565% and butadiene 45-35% of their mixture, and applying a layer of the emulsion to a paper base.
References Cited in the file of this patent UNITED STATES PATENTS 10 2,284,877 Martinez 2 June 2, 1942 2,410,792 Broeck Nov. 5, 1946 2,604,388 Staehle July 22, 1952
Claims (1)
1. A COMPOSITION OF MATTER COMPRISING A GELATIN-SILVER HALIDE PHOTOGRAPHIC EMULSION IN WHICH HAS BEEN INCORPORATED A STYRENE-BUTADIENE LATEX RESULTING FROM THE EMULSION POLYMERIZATION OF STYRENE AND BUTADIENE IN THE PROPORTIONS OF 55-65% OF THE FORMER AND 45-35% OF THE LATTER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US552989A US2865753A (en) | 1955-12-14 | 1955-12-14 | Photographic emulsions containing a styrene-butadiene latex and photographic paper made therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US552989A US2865753A (en) | 1955-12-14 | 1955-12-14 | Photographic emulsions containing a styrene-butadiene latex and photographic paper made therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2865753A true US2865753A (en) | 1958-12-23 |
Family
ID=24207659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US552989A Expired - Lifetime US2865753A (en) | 1955-12-14 | 1955-12-14 | Photographic emulsions containing a styrene-butadiene latex and photographic paper made therewith |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2865753A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011890A (en) * | 1958-07-21 | 1961-12-05 | Eastman Kodak Co | Photographic emulsions |
| US3079257A (en) * | 1957-08-30 | 1963-02-26 | Agfa Ag | Photographic materials containing acrylonitrile copolymers as matting agents |
| US3165411A (en) * | 1959-05-04 | 1965-01-12 | Eastman Kodak Co | Photographic products |
| US3220840A (en) * | 1960-07-01 | 1965-11-30 | Eastman Kodak Co | Inflatable photographic elements including an elastic silver halide emulsion, and process for making same |
| US3472673A (en) * | 1966-05-09 | 1969-10-14 | Mead Corp | Process for producing coating on paper base having electrophotographic properties |
| US3649336A (en) * | 1967-09-28 | 1972-03-14 | Agfa Gevaert Nv | Plural coated sheet material |
| US3885081A (en) * | 1967-09-28 | 1975-05-20 | Agfa Gevaert Nv | Sheet material |
| US4485170A (en) * | 1982-02-10 | 1984-11-27 | Fuji Photo Film Co., Ltd. | Photographic silver halide light-sensitive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2284877A (en) * | 1940-06-03 | 1942-06-02 | Eastman Kodak Co | Light sensitive color element |
| US2410792A (en) * | 1943-05-27 | 1946-11-05 | Wingfoot Corp | Coated cord |
| US2604388A (en) * | 1943-11-16 | 1952-07-22 | Eastman Kodak Co | Photosensitive coating |
-
1955
- 1955-12-14 US US552989A patent/US2865753A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2284877A (en) * | 1940-06-03 | 1942-06-02 | Eastman Kodak Co | Light sensitive color element |
| US2410792A (en) * | 1943-05-27 | 1946-11-05 | Wingfoot Corp | Coated cord |
| US2604388A (en) * | 1943-11-16 | 1952-07-22 | Eastman Kodak Co | Photosensitive coating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3079257A (en) * | 1957-08-30 | 1963-02-26 | Agfa Ag | Photographic materials containing acrylonitrile copolymers as matting agents |
| US3011890A (en) * | 1958-07-21 | 1961-12-05 | Eastman Kodak Co | Photographic emulsions |
| US3165411A (en) * | 1959-05-04 | 1965-01-12 | Eastman Kodak Co | Photographic products |
| US3220840A (en) * | 1960-07-01 | 1965-11-30 | Eastman Kodak Co | Inflatable photographic elements including an elastic silver halide emulsion, and process for making same |
| US3472673A (en) * | 1966-05-09 | 1969-10-14 | Mead Corp | Process for producing coating on paper base having electrophotographic properties |
| US3649336A (en) * | 1967-09-28 | 1972-03-14 | Agfa Gevaert Nv | Plural coated sheet material |
| US3885081A (en) * | 1967-09-28 | 1975-05-20 | Agfa Gevaert Nv | Sheet material |
| US4485170A (en) * | 1982-02-10 | 1984-11-27 | Fuji Photo Film Co., Ltd. | Photographic silver halide light-sensitive material |
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