US3453113A - Silver halide polyvinyl alcohol emulsions containing hardening agent - Google Patents
Silver halide polyvinyl alcohol emulsions containing hardening agent Download PDFInfo
- Publication number
- US3453113A US3453113A US504139A US3453113DA US3453113A US 3453113 A US3453113 A US 3453113A US 504139 A US504139 A US 504139A US 3453113D A US3453113D A US 3453113DA US 3453113 A US3453113 A US 3453113A
- Authority
- US
- United States
- Prior art keywords
- polyvinyl alcohol
- silver halide
- percent
- photographic
- emulsion
- 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 description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 title description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 title description 25
- -1 Silver halide Chemical class 0.000 title description 6
- 239000003795 chemical substances by application Substances 0.000 title description 5
- 229910052709 silver Inorganic materials 0.000 title description 5
- 239000004332 silver Substances 0.000 title description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 32
- 238000000576 coating method Methods 0.000 description 17
- 235000011007 phosphoric acid Nutrition 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000123 paper Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005406 washing Methods 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
Definitions
- This invention relates to photographic emulsions and more particularly to emulsions in which synthetic binders containing polyvinyl alcohol are employed, and to hardeners for use therein.
- Emulsions containing polyvinyl alcohol require the addition of hardening agents so that after coating of the emulsion upon the support or substrate, the photosensitive material can be exposed and then further processed by the usual procedures using aqueous photographic processing solutions. While a number of such materials have been available heretofore, they have certain disadvantages, such as hardening the emulsion system too rapidly, thus interfering with coating techniques; insufficient permeability of the resulting emulsion layer after coating and drying, so that developing solutions could not penetrate, and the like. Another disadvantage of some of these hardeners is their failure to harden the emulsion coating sufficiently to provide satisfactory mechanical stability during processing.
- Aqueous emulsions thus prepared have a long pre-coating shelf life without irreversibly gelling or hardening, and they can be stored at ordinary temperatures fora long time before coating on a support. During coating, tackiness of the emulsion coatings is eliminated without appreciably increasing the viscosity of the photographic emulsion.
- the emulsion After coating, the emulsion is sufiiciently hard to make it abrasion-resistant, while at the same time, the dry coating is permeable to aqueous solutions to such a degree that complete development, fixing and washing can occur. Additionally it is unexpectedly found that the photographic coating is further hardened during development when basic (alkaline) developer solutions are used.
- Polyvinyl alcohol is prepared by the hydrolysis (alcoholysis) of polyvinyl acetate. This process is ordinarily not carried to completion and it is to be understood that the polyvinyl alcohol polymers used herein can contain a proportion of unhydrolyzed acetate groups.
- the orthophosphoric acid is added to the photographic emulsion system containing polyvinyl alcohol during mixing of the emulsion and preferably prior to the addition of the soluble silver salt.
- an aqueous mixture containing polyvinyl alcohol in amount sufiicient to provide the desired binder properties for the ultimate photographic emulsion is acidified to a pH of the order of about 3.
- Dilute phosphoric acid is then added slowly and with stirring to provide a homogeneous mixture.
- a soluble silver salt e.g., silver nitrate
- Silver halide is formed in the usual manner.
- the emulsion may then if desired be kept at an elevated temperature for Ostwald ripening, following which it is coated, as on paper or a synthetic resin film substrate, or glass, in the usual way.
- the amount of polyvinyl alcohol employed in any particular emulsion system may vary, depending upon whether or not it is the only gelling agent employed in the particular emulsion system used. Commonly, 5 to 10 parts of polyvinyl alcohol of medium molecular weight as used for gelling fluids per 100 parts of water are used when this is the only synthetic hydrophilic peptizing colloid employed. About 1 to 20 percent of orthophosphoric acid, based upon the weight of polyvinyl alcohol employed, is used as a hardener. Conveniently, the phosphoric acid is added as an aqueous solution of the commonly available percent orthophosphoric acid. For photographic purposes, reagent grade material is used to avoid undesirable impurities.
- solutions of polyvinyl alcohol can be used for sizing paper, coatings on paper and cloth, cement or glue, etc. These can be prepared in concentrations of upwards of about 1 percent by weight; and orthophosphoric acid when added in amounts of about 1 to 20 percent based on the dry weight of the polyvinyl alcohol strengthens and hardens the coatings made therewith. Accordingly, the invention comprehends within its scope aqueous solutions of upwards of one percent by weight of polyvinyl alcohol, containing from 1 to 20 percent by weight of orthophosphoric acid, based on the dry weight of the polyvinyl alcohol.
- the molecular weight of the polyvinyl alcohol affects its water-solubility, as is known; lower molecular weight polymer may be soluble to as much as 20 to 30 percent by weight or more, while high molecular weight material is less soluble.
- the choice of molecular weight and concentration will depend on the end-use and one skilled in the art will have no difficulty in selecting the appropriate materials and amounts.
- EXAMPLE 2 A polyvinyl alcohol solution (104 parts of 9.6 percent aqueous solution) is acidified by the addition of 10 parts of 48 percent aqueous hydrobromic acid. To this is added 4 parts of 21 percent aqueous phosphoric acid, with good stirring. Thereafter all operations are conducted in the dark. A solution of 10 parts of 5.9 N silver nitrate in water is added with good stirring over a period of about 10 seconds, and the mixture is then further stirred well for several minutes. To this is added 4 parts of surfactant (as used in Example 1) and the mixture is stirred for an additional 3 minute period.
- Coatings of the resulting photographic emulsion are made upon baryta paper in the usual way.
- the coated paper is air dried and stored in light-proof containers.
- a dispersion of silver halide and binder adapted for use to prepare a photographic emulsion comprising an aqueous solution of polyvinyl alcohol containing a silver halide dispersed therein, together with from 1 to 20 percent of orthophosphoric acid, 'based on the dry weight of the said polyvinyl alcohol, dissolved therein, as a hardening agent for the said polyvinyl alcohol.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
United States Patent US. Cl. 96--111 1 Claim ABSTRACT OF THE DISCLOSURE orthophosphoric acid, when added to a photographic emulsion comprising an aqueous solution of polyvinyl alcohol with silver halide dispersed therein, produces optimum hardening.
This invention relates to photographic emulsions and more particularly to emulsions in which synthetic binders containing polyvinyl alcohol are employed, and to hardeners for use therein.
Much research work has been carried out heretofore in a search for synthetic materials which would be free from the disadvantages of gelatin for use in photographic applications. A number of materials have been developed which have the thermally reversible gelling properties of gelatin dispersions, and which can be used as binders for photographic emulsions. Among these is polyvinyl alcohol, which can be used as such, or with other water dispersible materials as a photographic emulsion gelling agent and binder.
Emulsions containing polyvinyl alcohol require the addition of hardening agents so that after coating of the emulsion upon the support or substrate, the photosensitive material can be exposed and then further processed by the usual procedures using aqueous photographic processing solutions. While a number of such materials have been available heretofore, they have certain disadvantages, such as hardening the emulsion system too rapidly, thus interfering with coating techniques; insufficient permeability of the resulting emulsion layer after coating and drying, so that developing solutions could not penetrate, and the like. Another disadvantage of some of these hardeners is their failure to harden the emulsion coating sufficiently to provide satisfactory mechanical stability during processing.
It is an object of this invention to provide novel photographic emulsions which contain polyvinyl alcohol as a gelling agent and binder therefor, and a new hardening agent and photographic materials using such emulsions.
In accordance with the above and other objects of the invention, it has been found that by the use of orthophosphoric acid as a hardening agent for photographic emulsion systems containing polyvinyl alcohol, very useful photographic materials can be prepared. Aqueous emulsions thus prepared have a long pre-coating shelf life without irreversibly gelling or hardening, and they can be stored at ordinary temperatures fora long time before coating on a support. During coating, tackiness of the emulsion coatings is eliminated without appreciably increasing the viscosity of the photographic emulsion. After coating, the emulsion is sufiiciently hard to make it abrasion-resistant, while at the same time, the dry coating is permeable to aqueous solutions to such a degree that complete development, fixing and washing can occur. Additionally it is unexpectedly found that the photographic coating is further hardened during development when basic (alkaline) developer solutions are used.
3,453,113 Patented July 1, 1969 ICC Polyvinyl alcohol is prepared by the hydrolysis (alcoholysis) of polyvinyl acetate. This process is ordinarily not carried to completion and it is to be understood that the polyvinyl alcohol polymers used herein can contain a proportion of unhydrolyzed acetate groups.
Broadly speaking, the orthophosphoric acid is added to the photographic emulsion system containing polyvinyl alcohol during mixing of the emulsion and preferably prior to the addition of the soluble silver salt. Thus for example an aqueous mixture containing polyvinyl alcohol in amount sufiicient to provide the desired binder properties for the ultimate photographic emulsion is acidified to a pH of the order of about 3. Dilute phosphoric acid is then added slowly and with stirring to provide a homogeneous mixture. In the dark, a soluble silver salt, e.g., silver nitrate, is added in desired amount with stirring. Silver halide is formed in the usual manner. The emulsion may then if desired be kept at an elevated temperature for Ostwald ripening, following which it is coated, as on paper or a synthetic resin film substrate, or glass, in the usual way.
The amount of polyvinyl alcohol employed in any particular emulsion system may vary, depending upon whether or not it is the only gelling agent employed in the particular emulsion system used. Commonly, 5 to 10 parts of polyvinyl alcohol of medium molecular weight as used for gelling fluids per 100 parts of water are used when this is the only synthetic hydrophilic peptizing colloid employed. About 1 to 20 percent of orthophosphoric acid, based upon the weight of polyvinyl alcohol employed, is used as a hardener. Conveniently, the phosphoric acid is added as an aqueous solution of the commonly available percent orthophosphoric acid. For photographic purposes, reagent grade material is used to avoid undesirable impurities.
In non-photographic applications, solutions of polyvinyl alcohol can be used for sizing paper, coatings on paper and cloth, cement or glue, etc. These can be prepared in concentrations of upwards of about 1 percent by weight; and orthophosphoric acid when added in amounts of about 1 to 20 percent based on the dry weight of the polyvinyl alcohol strengthens and hardens the coatings made therewith. Accordingly, the invention comprehends within its scope aqueous solutions of upwards of one percent by weight of polyvinyl alcohol, containing from 1 to 20 percent by weight of orthophosphoric acid, based on the dry weight of the polyvinyl alcohol.
The molecular weight of the polyvinyl alcohol affects its water-solubility, as is known; lower molecular weight polymer may be soluble to as much as 20 to 30 percent by weight or more, while high molecular weight material is less soluble. The choice of molecular weight and concentration will depend on the end-use and one skilled in the art will have no difficulty in selecting the appropriate materials and amounts.
The invention will now be illustrated by the following examples, in which all parts are by weight unless otherwise specified.
EXAMPLE 1 A well stirred mixture of polyethylenimine, 5 parts (50 percent aqueous solution, molecular weight=30 40,000) and polyvinyl alcohol, 62.5 parts (8 percent aqueous solution, available under the trade name Elvanol 72-51) is acidified to pH 3 by the addition of hydrobromic acid. To the well stirred mixture is added slowly 2 parts of dilute phosphoric acid (made by adding 0.5 part of 85 percent orthophosphoric acid to 1.5 parts of water), with thorough mixing to insure homogeneity. The mixture is then placed in the dark, and a solution of 5 parts of silver nitrate in 5 parts of water is added with thorough mixing over a period of about seconds. The mixture is further stirred for about 3 minutes. To this is added 1 part of surfactant solution (12 percent aqueous solution of Poly- Tergent J-300, a nonionic, water soluble polyether) and the mixture is stirred for an additional minute. The resulting emulsion is knife coated upon paper base, in the dark, and upon plastic film support, the coatings are air dried and stored in a dark place. All of the steps in the preparation of the emulsion are performed at or near room temperature.
When exposed to light through a negative in the usual way, and developed with the ordinary paper developing solutions, excellent prints with good contrast are obtained, the surface of the paper being semi-glossy and resistant to abrasion even during processing in the aqueous solutions.
EXAMPLE 2 A polyvinyl alcohol solution (104 parts of 9.6 percent aqueous solution) is acidified by the addition of 10 parts of 48 percent aqueous hydrobromic acid. To this is added 4 parts of 21 percent aqueous phosphoric acid, with good stirring. Thereafter all operations are conducted in the dark. A solution of 10 parts of 5.9 N silver nitrate in water is added with good stirring over a period of about 10 seconds, and the mixture is then further stirred well for several minutes. To this is added 4 parts of surfactant (as used in Example 1) and the mixture is stirred for an additional 3 minute period.
Coatings of the resulting photographic emulsion are made upon baryta paper in the usual way. The coated paper is air dried and stored in light-proof containers.
On exposure to light, using the paper as a printing medi-,
um under a photographic negative, followed by standard development with metol-hydroquinone developer and fixing, using sodium thiosulfate fixing solutions, excellent prints are obtained. These show good mechanical resistance to abrasion, together with excellent permeability for the aqueous developing and fixing solutions.
EXAMPLE 3 To 100 parts of a 10 percent aqueous solution of polyvinyl alcohol prepared from high molecular weight polyvinyl acetate by hydrolysis, the degree of hydrolysis being about percent, are added, with stirring, 3 parts of 50 percent aqueous orthophosphoric acid (d=l.335, prepared by diluting percent orthophosphoric acid as commercially available). The solution, after mixing, can be stored for days without gelling or hardening, at room temperature. When coated upon paper, the coating is stronger and tougher than a similar coating prepared with the same polyvinyl alcohol solution which does not contain orthophosphoric acid.
What is claimed is:
1. A dispersion of silver halide and binder adapted for use to prepare a photographic emulsion, comprising an aqueous solution of polyvinyl alcohol containing a silver halide dispersed therein, together with from 1 to 20 percent of orthophosphoric acid, 'based on the dry weight of the said polyvinyl alcohol, dissolved therein, as a hardening agent for the said polyvinyl alcohol.
References Cited UNITED STATES PATENTS 2,376,371 9/1943 Lowe et al 96-114 3,113,026 12/1963 Sprung 96-107 J. TRAVIS BROWN, Primary Examiner.
J. R. HIGHTOWER, Assistant Examiner.
US. Cl. X.R. 96114
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50413965A | 1965-10-23 | 1965-10-23 | |
| US6457670A | 1970-08-17 | 1970-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3453113A true US3453113A (en) | 1969-07-01 |
Family
ID=26744657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US504139A Expired - Lifetime US3453113A (en) | 1965-10-23 | 1965-10-23 | Silver halide polyvinyl alcohol emulsions containing hardening agent |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3453113A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038082A (en) * | 1973-08-30 | 1977-07-26 | Fuji Photo Film Co., Ltd. | Image-receiving material for color diffusion transfer comprising pva and polymethylol compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2376371A (en) * | 1943-09-11 | 1945-05-22 | Eastman Kodak Co | Polyvinyl alcohol emulsion coating |
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
-
1965
- 1965-10-23 US US504139A patent/US3453113A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2376371A (en) * | 1943-09-11 | 1945-05-22 | Eastman Kodak Co | Polyvinyl alcohol emulsion coating |
| US3113026A (en) * | 1959-01-19 | 1963-12-03 | Gen Aniline & Film Corp | Polyvinyl alcohol photographic silver halide emulsions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038082A (en) * | 1973-08-30 | 1977-07-26 | Fuji Photo Film Co., Ltd. | Image-receiving material for color diffusion transfer comprising pva and polymethylol compounds |
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