US2091713A - Developer - Google Patents

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Info

Publication number: US2091713A
Authority: US; United States
Prior art keywords: color; developer; para; phenylenediamine; image
Prior art date: 1935-02-27
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

US8518A

Inventor

Leopold D Mannes

Jr Leopold Godowsky

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.)

1935-02-27

Filing date

1935-02-27

Publication date

1937-08-31

1935-02-27 Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co

1935-02-27 Priority to US8518A priority Critical patent/US2091713A/en

1936-02-27 Priority to FR804471D priority patent/FR804471A/en

1937-08-31 Application granted granted Critical

1937-08-31 Publication of US2091713A publication Critical patent/US2091713A/en

1954-08-31 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 22
150000001875 compounds Chemical class 0.000 description 22
238000009740 moulding (composite fabrication) Methods 0.000 description 18
238000000034 method Methods 0.000 description 16
ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 13
ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 13
230000008569 process Effects 0.000 description 13
239000012670 alkaline solution Substances 0.000 description 11
230000003647 oxidation Effects 0.000 description 11
238000007254 oxidation reaction Methods 0.000 description 11
230000008878 coupling Effects 0.000 description 9
238000010168 coupling process Methods 0.000 description 9
238000005859 coupling reaction Methods 0.000 description 9
239000000839 emulsion Substances 0.000 description 9
-1 silver halide Chemical class 0.000 description 6
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
150000004982 aromatic amines Chemical class 0.000 description 5
230000009467 reduction Effects 0.000 description 5
229910052709 silver Inorganic materials 0.000 description 4
239000004332 silver Substances 0.000 description 4
239000000243 solution Substances 0.000 description 4
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
229940116357 potassium thiocyanate Drugs 0.000 description 3
150000003567 thiocyanates Chemical class 0.000 description 3
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
239000003513 alkali Substances 0.000 description 2
229910052700 potassium Inorganic materials 0.000 description 2
239000011591 potassium Substances 0.000 description 2
238000000926 separation method Methods 0.000 description 2
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
125000003277 amino group Chemical group 0.000 description 1
150000001491 aromatic compounds Chemical class 0.000 description 1
125000003118 aryl group Chemical group 0.000 description 1
239000002585 base Substances 0.000 description 1
230000008901 benefit Effects 0.000 description 1
150000001555 benzenes Chemical class 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
238000005187 foaming Methods 0.000 description 1
239000004615 ingredient Substances 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
238000012986 modification Methods 0.000 description 1
230000004048 modification Effects 0.000 description 1
150000003839 salts Chemical group 0.000 description 1
238000001228 spectrum Methods 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers

Definitions

This invention relates to photographic developers. and, more particularly, to developers having increased reduction potential.
Certain developers such as the para-phenylenediamines
developers are unsatisfactory for ordinary photographic use because of their low reduction potential.
the color-forming compound may be mixed with the developer, or may be incorporated in the sensitized emulsion prior to exposure. Such a process is disclosed in Fischer U. S. Patent No.
a film base coated with two or more silver halide emulsion layers, each of which is sensitized to a different region of the spectrum, is exposed to form a latent colorseparation image in each layer.
the film is developed in a developer in which an aromatic amine, such as para-phenylenediamine hydrochloride, is the developing ingredient and which contains a color-forming compound.
an aromatic amine such as para-phenylenediamine hydrochloride
the silver halide present in the emulsion is reduced to metallic silver and where this occurs, the para-phenylenediamine is oxidized.
the color-forming compound present in the developer is one which will combine with the oxidation product of the paraphenylenediamine to form a colored dye compound.
Formula 1 produces on development a blue-green 10.
Our invention is applicable to the formation of color pictures by any method in which a color is formed by coupling of the oxidation product of an aromatic amine developer with a color former.
the sensitized emulsion may be in one or more layers and may be on one or both sides of a film.
Our process may also be used with plates as well as films and with various types of color separation processes, for example, in which the 45 color separation negatives are exposed separately and later superposed to form a complete colored picture.
'Ihe 'colorforming compound may be present in the developer solution or it may be incorporated in the emulsion layer prior to exposure.
Our invention is not limited to the use of thiccyanates with color developers. We have found that a small amount of thiocyanate will increase the reduction potential of an aromatic amino quarter to 2 grams per liter of developer solution, while with ordinary para-phenylenediamine developers, amounts as high as 7 grams per liter have been used.
aromatic amino developers we intend to include the mono-, di-, and triamino aromatic compounds, of which the paraphenylenediamines are the compounds generally used.
the salt form such as the hydrochloride or the sulfate, is most desirable, due to its stability in the dry state.
These compounds may be substituted in the amino group or in the ring, forming the alkyl phenylenediamines, and the toluylenediamines.
a particular advantage of our process is the fact that it enables the direct development of color films to form a colored image. It is frequently necessary with such films to develop the film in an ordinary meto'l-hydroquinone developer to a black and white image and later convert this image by color development to a colored image.
the colored image may be obtained by direct development.
a process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a primary aryl amine developing agent, said aryl being of the benzene series, and a thiocyanate, and simultaneously coupling the oxidation product of the primary aryl amine developer with a color-forming compound.
a process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-form ing compound.
a process of producing a coloredphotographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-foaming compound originally present in the developer solution.
a process of producing a colored photographic image which comprises developing a latent ima'ge in an alkaline solutionto which has been added a p'ara-phenylenediamine' hydrochloride and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound.
a process of producing a, colored photographic image which comprises developing a latent image in an alkaline solution to which has been added a para-phenylenediamine hydrochloride and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound originally present in the developer solution.
Aprocess of producing a colored photo'- graphic image which comprises developing a. latent image in an alkaline solution containing a para-phenylenediamine and an alkali thiocyanate, and simultaneously coupling the oxidation product of the, para-phenylenediamine with a color-forming compound.
a process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and potassium thiocyanate and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound.
a process of producing a colored photographic image which comprises incorporating a color-forming compound in a sensitive emulsion, exposing said emulsion to form a latent image, and developing said latent image in a developer containing a para-phenylenediamine and a thiocyanate.
a process of producing a. colored photographic image which comprises incorporating a color-forming compound in a sensitive emulsion, exposing said emulsion to form a latent image, and developing said latent image in a developer containing a para-phenylenediamine salt and potassium thiocyanate.
a photographic developer comprising a para-phenylenediamine in alkaline solution, a color-forming compound and a thiocyanate.
a -photographic developer comprising a para-phenylenediamine in alkaline solution, a color-forming compound and an alkali thiocyanate.
a photographic developer comprising a para-phenylenediamine inorganic acid salt in alkaline solution, a color-forming compound, and
a photographic developer comprising a para-phenylenediamine hydrochloride in alkaline solution, a color-forming compound and a thiocyanate.
a photographic developer comprising a para-phenylenediamine salt in alkaline solution, a color-forming compound and potassium thiocyanate.

Landscapes

Physics & Mathematics (AREA)
General Physics & Mathematics (AREA)
Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

Patented Aug. 31, 1937' nnvsnom Leopold D. Mannes and Leopold Godowsky, In,

Rochester, N. Y.,

assllnors, by mesne assignments, to Eastman Kodak Company, Jersey City, N. 1., a corporation of New Jersey No Drawing. Application February 27, 1935,

. SerlalNo. 8,518

14 Claims.

This invention relates to photographic developers. and, more particularly, to developers having increased reduction potential.

Certain developers, such as the para-phenylenediamines, are unsatisfactory for ordinary photographic use because of their low reduction potential. In the production of natural color photographic plates or films, it is frequently desirable to use the para-phenylenediamines as developers and to form the colored image by coupling during developing the oxidation'pro'duct of the developer with a color-forming compound. The color-forming compound may be mixed with the developer, or may be incorporated in the sensitized emulsion prior to exposure. Such a process is disclosed in Fischer U. S. Patent No.

1,102,028, June 30, 1914. The para-phenylenediamine developers used in this process have a low reduction potential and it is, therefore, necessary to increase the time of development in order to obtain a satisfactory picture.

It is an object of the present invention to provide a method for increasing the reduction potential of aromatic amino developers, particularly color developers. It is a further object to provide means for decreasing the time of development when using the aromatic amines as developers. It is a still further object to provide means for increasing the color gamma of natural color pictures on development.

These objects are accomplished by the present invention by using thiocyanates mixed with the developer. I

According to our invention a film base coated with two or more silver halide emulsion layers, each of which is sensitized to a different region of the spectrum, is exposed to form a latent colorseparation image in each layer. The film is developed in a developer in which an aromatic amine, such as para-phenylenediamine hydrochloride, is the developing ingredient and which contains a color-forming compound. On development of the latent image, the silver halide present in the emulsion is reduced to metallic silver and where this occurs, the para-phenylenediamine is oxidized. The color-forming compound present in the developer is one which will combine with the oxidation product of the paraphenylenediamine to form a colored dye compound. Since the oxidation product is formed only where the silver halide is' reduced, a dye is formed onlyat such points. This developer when used alone for developing negative films is not entirely satisfactory due to the length of time required for the development. We have found that by adding a small amount of a thiocyanate,- such as potassium thiocyanata'to the developer, the reductionxpotentlal'of the developer is increased to such an extent that a development takes place in the time ordinarily.required for 5 development by the use of a metol-hydroquinone type 01' developer.

The following formulas illustrate developers which may be used according to our process.

Formula 1 produces on development a blue-green 10.

image and Formula 2 produces a magenta image.

Water to make cublc centimeters" 1000 (I?) (Added to ((1)) Brom-thioindoxyl gram 1 Methanol cubic centimeters Various thiocyanates, such as potassium, sodi- 35 um and ammonium may be used.

Our invention is applicable to the formation of color pictures by any method in which a color is formed by coupling of the oxidation product of an aromatic amine developer with a color former. The sensitized emulsion may be in one or more layers and may be on one or both sides of a film. Our process may also be used with plates as well as films and with various types of color separation processes, for example, in which the 45 color separation negatives are exposed separately and later superposed to form a complete colored picture. 'Ihe 'colorforming compound may be present in the developer solution or it may be incorporated in the emulsion layer prior to exposure.

Our invention is not limited to the use of thiccyanates with color developers. We have found that a small amount of thiocyanate will increase the reduction potential of an aromatic amino quarter to 2 grams per liter of developer solution, while with ordinary para-phenylenediamine developers, amounts as high as 7 grams per liter have been used.

In referring to the aromatic amino developers, we intend to include the mono-, di-, and triamino aromatic compounds, of which the paraphenylenediamines are the compounds generally used. The salt form, such as the hydrochloride or the sulfate, is most desirable, due to its stability in the dry state. These compounds may be substituted in the amino group or in the ring, forming the alkyl phenylenediamines, and the toluylenediamines.

A particular advantage of our process is the fact that it enables the direct development of color films to form a colored image. It is frequently necessary with such films to develop the film in an ordinary meto'l-hydroquinone developer to a black and white image and later convert this image by color development to a colored image. By the use of our method in which thiocyanates are added to the developer, the colored image may be obtained by direct development.

Our invention is not limited to the specific examples disclosed, but may be used in numerous other forms and modifications.

Having thus described our invention, what we declare is new and desire to secure by Letters Patent of the United States is:

1. A process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a primary aryl amine developing agent, said aryl being of the benzene series, and a thiocyanate, and simultaneously coupling the oxidation product of the primary aryl amine developer with a color-forming compound. v

2. A process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-form ing compound.

3. A process of producing a coloredphotographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-foaming compound originally present in the developer solution.

4. A process of producing a colored photographic image which comprises developing a latent ima'ge in an alkaline solutionto which has been added a p'ara-phenylenediamine' hydrochloride and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound.

5. A process of producing a, colored photographic image which comprises developing a latent image in an alkaline solution to which has been added a para-phenylenediamine hydrochloride and a thiocyanate, and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound originally present in the developer solution.

6. Aprocess of producing a colored photo'- graphic image which comprises developing a. latent image in an alkaline solution containing a para-phenylenediamine and an alkali thiocyanate, and simultaneously coupling the oxidation product of the, para-phenylenediamine with a color-forming compound.

7. A process of producing a colored photographic image which comprises developing a latent image in an alkaline solution containing a para-phenylenediamine and potassium thiocyanate and simultaneously coupling the oxidation product of the para-phenylenediamine with a color-forming compound.

8. A process of producing a colored photographic image which comprises incorporating a color-forming compound in a sensitive emulsion, exposing said emulsion to form a latent image, and developing said latent image in a developer containing a para-phenylenediamine and a thiocyanate. I

9. A process of producing a. colored photographic image which comprises incorporating a color-forming compound in a sensitive emulsion, exposing said emulsion to form a latent image, and developing said latent image in a developer containing a para-phenylenediamine salt and potassium thiocyanate.

10. A photographic developer comprising a para-phenylenediamine in alkaline solution, a color-forming compound and a thiocyanate.

11. A -photographic developer comprising a para-phenylenediamine in alkaline solution, a color-forming compound and an alkali thiocyanate.

12. A photographic developer comprising a para-phenylenediamine inorganic acid salt in alkaline solution, a color-forming compound, and

a thiocyanate.

13. A photographic developer comprising a para-phenylenediamine hydrochloride in alkaline solution, a color-forming compound and a thiocyanate.

14. A photographic developer comprising a para-phenylenediamine salt in alkaline solution, a color-forming compound and potassium thiocyanate.

LEOPOLD D. MANNES. LEOPOLD GODOWSKY, JR.

US8518A 1935-02-27 1935-02-27 Developer Expired - Lifetime US2091713A (en)

Priority Applications (2)

Application Number	Priority Date	Filing Date	Title
US8518A US2091713A (en)	1935-02-27	1935-02-27	Developer
FR804471D FR804471A (en)	1935-02-27	1936-02-27	Photographic developers

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
US8518A US2091713A (en)	1935-02-27	1935-02-27	Developer

Publications (1)

Publication Number	Publication Date
US2091713A true US2091713A (en)	1937-08-31

Family

ID=21732048

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US8518A Expired - Lifetime US2091713A (en)	1935-02-27	1935-02-27	Developer

Country Status (2)

Country	Link
US (1)	US2091713A (en)
FR (1)	FR804471A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2553498A (en) *	1947-11-18	1951-05-15	Gen Aniline & Film Corp	First developer for multilayer color film of the reversal type
US2665986A (en) *	1939-11-02	1954-01-12	Gevaert Photo Prod Nv	Process of producing colored reversal images
US5079133A (en) *	1986-04-11	1992-01-07	Fuji Photo Film Co., Ltd.	Silver halide color photographic material

1935
- 1935-02-27 US US8518A patent/US2091713A/en not_active Expired - Lifetime
1936
- 1936-02-27 FR FR804471D patent/FR804471A/en not_active Expired

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2665986A (en) *	1939-11-02	1954-01-12	Gevaert Photo Prod Nv	Process of producing colored reversal images
US2553498A (en) *	1947-11-18	1951-05-15	Gen Aniline & Film Corp	First developer for multilayer color film of the reversal type
DE968447C (en) *	1947-11-18	1958-02-20	Gen Aniline & Film Corp	Process for the uniform development of exposed, multilayer color reversal films
US5079133A (en) *	1986-04-11	1992-01-07	Fuji Photo Film Co., Ltd.	Silver halide color photographic material

Also Published As

Publication number	Publication date
FR804471A (en)	1936-10-24

Publication	Publication Date	Title
US2367531A (en)	1945-01-16	Acylaminophenol photographic couplers
US3520689A (en)	1970-07-14	Color developing process utilizing pyridinium salts
US3520690A (en)	1970-07-14	Process for controlling dye gradation in color photographic element
US2360290A (en)	1944-10-10	Preventing formation of color fog in emulsions
US2313586A (en)	1943-03-09	Hydroxynaphthoic acid amide coupler
US3141771A (en)	1964-07-21	Aldehyde scavengers for photographic silver halide developers
US2675314A (en)	1954-04-13	Antistain agents for photographic color materials
US2403721A (en)	1946-07-09	Preventing color fog in photographic material
US3128182A (en)	1964-04-07	Silver halide solvent containing developers and process
US2482546A (en)	1949-09-20	Phenoxyalkylamines as accelerators for photographic developers
US2364675A (en)	1944-12-12	Color forming compounds containing sulphonamide groups
US2453661A (en)	1948-11-09	Colored couplers
US2933391A (en)	1960-04-19	Photographic emulsions containing 5-pyrazolone coupler compounds
US3246987A (en)	1966-04-19	Method for elimination of reversal reexposure in processing photographic elements
US3547640A (en)	1970-12-15	Multicolor photographic elements
US2694008A (en)	1954-11-09	Process for the production of colored masks in photographic color material
US2266452A (en)	1941-12-16	Nitronaphthol coupler for color photography
US2091713A (en)	1937-08-31	Developer
US2518739A (en)	1950-08-15	Method of masking photographic color images
US3189452A (en)	1965-06-15	Color-forming photographic process utilizing a bleach-fix followed by a bleach
US3489566A (en)	1970-01-13	Magneta color developer solutions
US3832179A (en)	1974-08-27	Inhibition of fog in photographic color development
US2113330A (en)	1938-04-05	Color-forming developers
US2295008A (en)	1942-09-08	Photographic color forming compound
JPS5860740A (en)	1983-04-11	Photographic contrast intensifier