US2604399A

US2604399A - Photographic developers comprising bis-(di-hydroxyalkyl aminomethyl)-hydroquinones

Info

Publication number: US2604399A
Application number: US103532A
Authority: US
Inventors: Thomas S Donovan; Frederic R Bean
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1949-07-07
Filing date: 1949-07-07
Publication date: 1952-07-22
Anticipated expiration: 1969-07-22

Description

Patented July 22, 1952 PHOTOGRAPHIC DEVELOPERS COMPRISING BIS- (DI HYDROXYALKYL AMINOMETIL. YL) -HYDROQUINON ES Thomas S. Donovan and Frederic R. Bean, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N.

Jersey Y., a corporation of New 'No Drawing. Application July 7,1949,

Serial No. 103,532

This invention relatesto photographic developers and-more particularly to photographic developing solutions.

Prominent among the developing agents now 'empolyed in the rapid development of 'photographic images are those comprising hydroquinone and Elon (p -N-methylaminophenol). While various formulas of these developers are excellently suited for general" photographic use, they have notbeen outstanding where developers: ofincreased water solubility are: required. 7

For example, certain aqueous photographic developer solutions comprising hydroquinone and Elon, give rise. to the formation of a precipitate after-the solutions have been allowed to stand for-a time. s

Photographic developers which possess this desired water solubility would represent a substantial advance in the art, if such developers retained muchof the developing activity exercised byr hydroquinone.

It is, therefore, an object of our invention to provide photographic developers which possess Water solubility of a high degree. A further object is to provide photographic developerswhich, in addition to having a high degree of water solubility, have suflicient developing activity (ability to reduce silver halide) to warrant their use in developing solutions. Other objects will become apparent from the following description and examples.

According to our invention we accomplish the above objects by providing photographic developer solutions comprising a bis-[di-(hydroxyalkyl) aminomethyl] hydroquinone.

The bis- [di- (hydroxyalkyl) aminomethyllhydroquinones useful in practicing our invention can advantageously be represented by the following general formula:

wherein R and R1 each represents a hydroxyalkyl group containing from 2 to 3 carbon atoms, Compounds represented by the, above formula which have been. found to' be especially 12 Claims.

useful for the purposes of our invention include those represented by the following formulas:

I CHiCHr-OH $Hs HO-CHCH:

NCH

HO-CHCH I OH. CH: 1

2,=-bis-[di- (B-hydroxyisopropyl) aminomethyl hydroqumone on I l omcnlcm on *CHr-N photographic developer formula useful in prac-' ticing our invention:

EXAMPLEI Elon ('p-(N methylarnino) phenol) grams 2.5 2,5-bis- [di (flhydroxyethyl) aminomethyl] hydroquinone oxalate grams 2.5

Sodium sulfite (anhydrous) do 75.0 Sodium carbonate (anhydrous) do 25.0 Potassium bromide do 1.5 Water to liters 1.0

This developer solution was used to develop 5'0 motion-picture positive-film;

The compounds represented j' by the above 3 EXAMPLEZ Another formula which has been found useful in practicing our invention is:

2,5-bis- [di- (flhydroxyethyl) aminomethyll hydroquinone oxlate grams 5.0 Sodium sulfite (anhydrous) do 75.0 Sodium carbonate (anhydrous) do 25.0 Potassium 'bromide i do 1.5 Water to; i liters 1.0

Photographic developer formulas other than those illustrated above can beemployed to advantage. Both the amount and type of hydroquinine developing agent can be varied to suit the requirements of the operator. The above formulas are merely illustrative'and are'not intended to limit our invention. I

The developing agents represented: by the above general formula are especially useful in the preparation of concentrated .photographic W developer formulas which find use in the field of The developers coming X-ray photography. within the scope of the present invention are characterized by their excellent solubility in water, a property which is much desired for such concentrated photographic. formulas. Whereas the conventional I-IQ-MQ (hydroquinone-Elon) concentrated developer solutions give rise to precipitates on standing, the developer solutions of the present invention donot show a precipitate at even higher concentrations. Typical concentrated developer formulas in which the hydroquinone compounds of our invention can be used includethose illustrated in the application of F. R. Bean; 'Serial'No. 94,510,'filed May 20, 1949, now U. S. Patent 2,578,281, issued December 11,. 1951. Such solutions generally comprise from about 50 to '75 grams of phenolic developer per liter of solution, although many of the hydroquinone compounds of, our invention permit even higher concentrations of phenolic developers to be used. The hydroquinone compounds represented by the above general formula can also be usedin tanning developer solutions, although usually less efiicaciously than hydroquinone itself, we have found.

The'following examples illustrate the method of preparation of typical hydroquinone compounds coming within the scope of our invention.

EXAMPLE 3 2,5 bisldi- (fi-hydhozyeth'ylamz'no) ethyl] hydroquinone oxalate 55 g. of hydroquinonewere dissolved in 125 cc. of water and 105 g'. of diethanolamine were added. The solution-was cooled-to C., 87 cc. of a 37 per cent formalin solution were added dropwise with stirring over a period of 30 minutes, and the solution was then stirred at room temperature for an additional hour. The reaction mixture was concentrated under. a vacuum to a thin syrup, 500 cc. of acetone added, and the acetone solution made acid to Congo Red with oxalic acid. The product crystallized as fine, white prisms melting at 196197 C. (with decomposition) They were very soluble in water.

2,5-bis Edi-(13 hydroxyisopropyl) aminom ethyll hydroquinone a 28 g. of hydroquinone were dissolved in 125 cc.

of a 75% solution of ethyl alcohol, and-7'7 g. of diisopropanolamine were added. "The solution was cooled to 15 C,., and 44 cc. of 37 per cent formalin were added dropwise with stirring. The mixture was then warmed on a steam bath for 30 minutes and the alcohol removed by evaporation. Thesyrupy residue was taken up in 150 cc. of water, the solution treated with decolorizing carbon and filtered. From the filtrate, on standing, there separated a tan crystalline solid which wasrecrystalizd' from ethanol. The crystals melted at 180-'182 (land were soluble in water, acids, alkalies, and alcohol. They were essentially insoluble in ether or benzene.

-- Other hydroquinone compounds useful in practicing our invention can be prepared by interacting hydroquinone, formaldehyde and other hydroalkylamines in the manner described above. The hydroquinone compounds of our invention can be mixed with the usual strongly alkaline v ber, resins, etc.

'materials employed in photographic developer solutions to give a dry mixture, and this mixture can then be dissolved in water to give a solution useful in preparing the desired developing formulas, i. e. the usual constituents employed in photographic formulas can then be added. The ratio of materials added to the mixture correspond to those given in the above formulas, although other known ratios of developing agent to alkali can be used to advantage, as. set forth above, the particular'ratios desired can be varied to suit the requirements of the operator.

The bis-Edi (hydroxyalkyl) aminomethyllhydroguinones of our invention can also be used as oxidationinhibitorsj for gasoline, fatty oils, rub- They can also'be efiicaciously used'in processes for oxidatively dyeing wool or fur, e. g. in the former their dilute aqueous alkaline. solutions (or bysoaking the object to be dyed in an alcoholic solution of the hydro wherein R and R1 represents a hydr'oxyalkyl group} f 2. A photographic silver halide developer solution comprising as the active developing agent an acid addition salt of a compound selected from those represented by the following general formula:

R om-N N-CHa R, DELL} wherein R and R1each representsa-hydroxalkyl group containing from 2 to '3 'carbon'atoms.

3. A photographic silver halide developer solution comprising as the active developing agent an acid addition salt of a compound selected from those represented by the following general formula:

wherein R and R1 each represents a p-hydroxyalkyl group containing from 2 to 3 carbon atoms.

4. A photographic silver halide developer solution comprising as the active developing agent an acid addition salt of the compound represented by the following formula:

HO-CHzCH1 CHaCHr-OH N-CH HO-CHzCHa 5. A photographic silver halide developer solution comprising as the active developing agent an acid addition salt of the compound represented by the following formula:

OH: OH

CHzCH-OH OH:

| CHg-N HO-CHCH;

OHaCH-OH N-CHz CHI HO-OHC 6. A photographic silver halide developer solution comprising as the active developing agent an acid addition salt of the compound represented by the following formula:

CHr-N N-CH HO-CHzCHzCHg 7. A solid mixture of chemicals useful for forming a photographic silver halide developer solution by dissolving in water comprising as a developing agent an acid addition salt of a compound selected from those represented by the following general formula:

CHz-N wherein R and R1 each represents a hydroxyalkyl group, and a strongly alkaline material.

8. A solid mixture of chemicals useful for forming a photographic silver halide developer solu tion by dissolving in water comprising as a developing agent an acid addition salt of a compound selected from those represented by the following general'formula:

wherein R and R1 each represents a hydroxyalkyl group containing from 2 to 3 carbon atoms, and a strongly alkaline material.

9. A solid mixture of chemicals useful for forming a photographic silver halide developer solution by dissolving in water comprising as a developing agent an acid addition salt of a compound selected from those represented by the following general formula:

CH2--N/ o aCHa-OH CHr-N HO-CHzOHz and a strongly alkaline material.

11. A solid mixture of chemicals useful for forming a photographic silver halide developer solution by dissolving in water comprising as a developing agent an acid addition salt of the compound represented by the following formula:

CH2 H-OH CH: CH

HO-JJHCHa CHzCH-OH N--CH2 OH: H 0-030 2 0H Ha and a strongly alkaline material.

12. A solid mixture of chemicals useful for forming a photographic silver halide developer solution by dissolving in water comprising as a developing agent an acid addition salt of the compound represented by the following formula:

l CHgOHzCHg-OH HO-CHzCHzCHr N-CHa BIO-OHzCH OH;

and a strongly alkaline material.

THOMAS S. DONOVAN. FREDERIC R. BEAN.

(References on followingpage) 2,304,953 Peterson Dec.15, 1942 7; 8.; REFERENCES CITED V',OfI-I-IER ;EEFERENCES The following references are of record in the Henn'eyf a hd; Dufilefl- Handbook of Pho file of this patent: tography, McGraw HilLNew York, 1939; pages- UNITED STATES PATENTS 5 328, 2 ,and 334 cited. r w 1 Number Name Date 2,163,166 Wilmanns et a1 June 20, 1939

Claims

1. A PHOTOGRAPHIC SILVER HALIDE DEVELOPER SOLUTION COMPRISING AS THE ACTIVE DEVELOPING AGENT AN ACID ADDITION SALT OF A COMPOUND SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: