US2139774A - Sensitizing and hardening photographic emulsions - Google Patents

Sensitizing and hardening photographic emulsions Download PDF

Info

Publication number: US2139774A
Authority: US; United States
Prior art keywords: emulsion; hardening; sensitizing; emulsions; gelatin
Prior art date: 1936-07-10
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

Application number

US90000A

Other languages

English (en)

Inventor

Samuel E Sheppard

Robert C Houck

Raymond H Lambert

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Eastman Kodak Co

Original Assignee

Eastman Kodak Co

Priority date (The priority date 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 date listed.)

1936-07-10

Filing date

1936-07-10

Publication date

1938-12-13

1936-07-10 Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co

1936-07-10 Priority to US90000A priority Critical patent/US2139774A/en

1937-07-10 Priority to DE1937K0147221 priority patent/DE696896C/de

1937-07-10 Priority to FR824219D priority patent/FR824219A/fr

1937-07-10 Priority to GB19172/37A priority patent/GB479419A/en

1938-12-13 Application granted granted Critical

1938-12-13 Publication of US2139774A publication Critical patent/US2139774A/en

1955-12-13 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000000839 emulsion Substances 0.000 title description 55
230000001235 sensitizing effect Effects 0.000 title description 7
239000003795 chemical substances by application Substances 0.000 description 15
238000000034 method Methods 0.000 description 13
238000011534 incubation Methods 0.000 description 12
108010010803 Gelatin Proteins 0.000 description 11
229920000159 gelatin Polymers 0.000 description 11
239000008273 gelatin Substances 0.000 description 11
235000019322 gelatine Nutrition 0.000 description 11
235000011852 gelatine desserts Nutrition 0.000 description 11
230000008569 process Effects 0.000 description 9
229910052709 silver Inorganic materials 0.000 description 8
239000004332 silver Substances 0.000 description 8
230000029087 digestion Effects 0.000 description 7
239000011248 coating agent Substances 0.000 description 6
238000000576 coating method Methods 0.000 description 6
238000001035 drying Methods 0.000 description 6
238000000209 wet digestion Methods 0.000 description 6
238000010438 heat treatment Methods 0.000 description 5
-1 hydroxy aldehydes Chemical class 0.000 description 5
238000002844 melting Methods 0.000 description 5
230000008018 melting Effects 0.000 description 5
OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 4
WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
230000001376 precipitating effect Effects 0.000 description 3
230000005070 ripening Effects 0.000 description 3
230000035945 sensitivity Effects 0.000 description 3
230000008961 swelling Effects 0.000 description 3
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
230000009471 action Effects 0.000 description 2
150000001875 compounds Chemical class 0.000 description 2
VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
206010010071 Coma Diseases 0.000 description 1
206010070834 Sensitisation Diseases 0.000 description 1
BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
150000001299 aldehydes Chemical class 0.000 description 1
229910021529 ammonia Inorganic materials 0.000 description 1
230000006399 behavior Effects 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
230000008859 change Effects 0.000 description 1
239000003153 chemical reaction reagent Substances 0.000 description 1
OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
238000000586 desensitisation Methods 0.000 description 1
230000006866 deterioration Effects 0.000 description 1
NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
239000004312 hexamethylene tetramine Substances 0.000 description 1
235000010299 hexamethylene tetramine Nutrition 0.000 description 1
WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
229960004011 methenamine Drugs 0.000 description 1
239000000203 mixture Substances 0.000 description 1
150000002972 pentoses Chemical class 0.000 description 1
230000000704 physical effect Effects 0.000 description 1
230000009467 reduction Effects 0.000 description 1
230000008313 sensitization Effects 0.000 description 1
HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 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

This invention relates to finishing photographic emulsions and particularly, to sensitizing and hardening gelatino-silver halide emulsions.
a gelatino-silver halide emulsion when first mixed is quite slow or insensitive, and unsatisfactory for making fast negative emulsions.
the emulsion mixture is, therefore, digested or ripened in orderto increase the sensitivity.
This ripening is ordinarily accomplished by the action of heat or by digestion with ammonia, either alone or in combination with heating. After treatment in this way the emulsion may be jelled and set and then re-melted and coated on the emulsion support.
the hardening agent is added at some period subsequent to the digestion, before coating the emulsion on the support.
the degree of hardening produced in this way is not complete after drying the product, but-a greater or lesser amount of so-called after hardening occurs on storage 5 of the plates or films. This may continue through a period of months'and may equal or surpass in degree the initial hardening on first drying. This after hardening, therefore, gives rise to a product whose properties are variable with time unless an inconvenientiy long period of storage prior to use is involved.
One consequence of this is generally reduction of speed of development, but other objectionable changes in photographic properties may ensue.
a further objection is that it is necessary to repeatedly subject samples of the plates or films to incubation tests in order to ascertain the amount of hardening that has taken place.'
an object of the present invention to provide a means for eliminating after hardening and for producing a more stable emulsion which will show less change in regard to sensitometric and physical properties, such as hardening and swelling, on storage.
a further object is to provide a novel method for hardening photographic emulsions.
a still further object is to provide a photographic emulsion which will be resistant to relatively high temperatures without objectionable fogging or de-sensitizing. Other objects will appear hereinafter.
the plate or film is then subjected to the heat treatment described below and the combined sensitizing and hardening action performed in this way.
This dry digestion or moist incubation has a number of advantages over the usual wet digestion in which the emulsions are ripened prior to addition of the hardening agent, in that the progress of the hardening is more conveniently controlled and that there is less tendency to increased fogging with increasing sensitization. This is shown by the following tables indicating the speed of plates, subjected to digestion and obtained by moist incubation (for 3.5 hours) was nearly, twice that obtained by wet digestion (at twenty minutes) for a corresponding amount of fog formation.
melting point is meant the temperature at which the emulsion or gelatin dissolves in water on heating the water.
the temperature of our treatment may be greater or less than 70 C. and may vary from about 40 C. to
the relative humidity may also vary somewhat within the range of about 50% to 80%, depending upon the amount and nature of the hardening agent used.
the temperature of treatment is preferably 60 C. to 70 0., and the relative humidity therefor between 50% and 80%.
the process of hardening gelatino silver halide emulsions and substantially eliminating after-hardening which comprises adding a hardening agent to the emulsion, coating the emulsion on a support and drying it, and subjecting the emulsion to moist incubation at a relative humidity of between 50% and 80% and a temperature of between 40 C. and 90 C. conjointly with ripening, for such length of time as will bring the emulsion to substantially uniform hardness.

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)
Application Of Or Painting With Fluid Materials (AREA)
Silver Salt Photography Or Processing Solution Therefor (AREA)
Paints Or Removers (AREA)
Processes Of Treating Macromolecular Substances (AREA)

US90000A 1936-07-10 1936-07-10 Sensitizing and hardening photographic emulsions Expired - Lifetime US2139774A (en)

Priority Applications (4)

Application Number	Priority Date	Filing Date	Title
US90000A US2139774A (en)	1936-07-10	1936-07-10	Sensitizing and hardening photographic emulsions
DE1937K0147221 DE696896C (de)	1936-07-10	1937-07-10	ographischen Halogensilbergelatineemulsionen
FR824219D FR824219A (fr)	1936-07-10	1937-07-10	Perfectionnements aux émulsions photographiques
GB19172/37A GB479419A (en)	1936-07-10	1937-07-10	Improvements in ripening and hardening photographic emulsions

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
US90000A US2139774A (en)	1936-07-10	1936-07-10	Sensitizing and hardening photographic emulsions

Publications (1)

Publication Number	Publication Date
US2139774A true US2139774A (en)	1938-12-13

Family

ID=22220603

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US90000A Expired - Lifetime US2139774A (en)	1936-07-10	1936-07-10	Sensitizing and hardening photographic emulsions

Country Status (4)

Country	Link
US (1)	US2139774A (fr)
DE (1)	DE696896C (fr)
FR (1)	FR824219A (fr)
GB (1)	GB479419A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2441440A (en) *	1945-01-25	1948-05-11	Du Pont	Silver halide photographic emulsions of enhanced light sensitivity
US2493838A (en) *	1945-07-19	1950-01-10	Bennett F Terry	Photoprinting processes
US2614930A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing polyvinyl alcohol-silver halide photographic emulsions
US2614931A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing cellulose ester-silver-halide photographic emulsions
US2614929A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing photographic emulsions
US2728662A (en) *	1947-08-13	1955-12-27	Eastman Kodak Co	Method of preparing photographic emulsions
US3047394A (en) *	1958-08-01	1962-07-31	Eastman Kodak Co	Photosensitive products containing therein layers hardened by bisepoxides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2640752A (en) *	1949-11-30	1953-06-02	Ethicon Suture Lab Inc	Process of making sutures
US2938763A (en) *	1956-02-20	1960-05-31	Jr Edward H Harris	Tanning with acetonylacetone

1936
- 1936-07-10 US US90000A patent/US2139774A/en not_active Expired - Lifetime
1937
- 1937-07-10 GB GB19172/37A patent/GB479419A/en not_active Expired
- 1937-07-10 DE DE1937K0147221 patent/DE696896C/de not_active Expired
- 1937-07-10 FR FR824219D patent/FR824219A/fr not_active Expired

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2441440A (en) *	1945-01-25	1948-05-11	Du Pont	Silver halide photographic emulsions of enhanced light sensitivity
US2493838A (en) *	1945-07-19	1950-01-10	Bennett F Terry	Photoprinting processes
US2614930A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing polyvinyl alcohol-silver halide photographic emulsions
US2614931A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing cellulose ester-silver-halide photographic emulsions
US2614929A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing photographic emulsions
US2614928A (en) *	1947-08-13	1952-10-21	Eastman Kodak Co	Method of preparing photographic emulsions
US2728662A (en) *	1947-08-13	1955-12-27	Eastman Kodak Co	Method of preparing photographic emulsions
US3047394A (en) *	1958-08-01	1962-07-31	Eastman Kodak Co	Photosensitive products containing therein layers hardened by bisepoxides

Also Published As

Publication number	Publication date
GB479419A (en)	1938-02-04
DE696896C (de)	1940-10-02
FR824219A (fr)	1938-02-04

Publication	Publication Date	Title
US2592368A (en)	1952-04-08	Gelatine silver halide emulsion layer containing a dihydroxy diphenyl tanning developing agent
US3320069A (en)	1967-05-16	Sulfur group sensitized emulsions
US1600736A (en)	1926-09-21	Art of light-sensitive photographic materials
US2592250A (en)	1952-04-08	Photographic silver bromide emulsion containing some silver iodide
US3687698A (en)	1972-08-29	Nonwandering hardening compounds and their use
US2310223A (en)	1943-02-09	Liquid hardener solution
US3226234A (en)	1965-12-28	Hardening photographic layers containing proteins
US2271622A (en)	1942-02-03	Photographic emulsion
US1870354A (en)	1932-08-09	Photographic gelatine layer
US2169513A (en)	1939-08-15	Process for hardening albuminous substances
US2591542A (en)	1952-04-01	Hardened photographic film of improved photographic properties
GB479419A (en)	1938-02-04	Improvements in ripening and hardening photographic emulsions
US3539353A (en)	1970-11-10	Poly(sulfoalkyl) gelatin
US2843491A (en)	1958-07-15	2-mercapto-1, 3, 4-oxadiazoles as antifoggants
US2227982A (en)	1941-01-07	Method of hardening photographic gelatin
US2553506A (en)	1951-05-15	Hardened gelatino-silver halede
US3157506A (en)	1964-11-17	Photographic film base subbed with acid-cooked pigskin gelatin
US3420667A (en)	1969-01-07	Substituted quinones and dimine quinones as silver halide sensitizers
US2037744A (en)	1936-04-21	Curing laminated sheeting
US2740713A (en)	1956-04-03	Sensitization of photographic emulsions
US3647458A (en)	1972-03-07	Solarization of silver halide photographic emulsions
US2534599A (en)	1950-12-19	Stabilized gelatino silver halide photographic emulsion
US2735769A (en)	1956-02-21	Stabilized photographic silver halede
US2739062A (en)	1956-03-20	Method of sizing photographic paper and resultant product
US2394600A (en)	1946-02-12	Substituted acid amide antifoggants