US2541889A - Alkyl ethers of polyhydroxyaralkylamines as accelerators - Google Patents

Description

Patented Feb. 13, 1951 I ALKYL ETHERS OF POLYHYDROXYARAL KYLAMINES AS ACCELERATORS Ivy V. Bunyan, Binghamton, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing.

12 Claims.

1 a This invention relates to photographic developers and particularly to alkyl ethers of polyhydroxyaralkylamines.

It is well'known that various amines, such as primary and secondary alkyl and alkylene amines containing from 3 to 7 carbon atoms may be added to photographic black and white and color developin solutions for the purpose of increasing the rate of development. In other words, these amines accelerate the development so as to cause the developing agent to form the image (silver or color image) more rapidly than is possible without the presence of such amines.

Although developing solutions containing such amines out the developing time to 12-15 minutes, such period is still unsatisfactory where large scale operations areinvolved, as in commercial processing where time is of the essence. It has been established that aralkylamines and phenoxyaralkylamines in which the aminoalkyl group contains from 2 to 3 carbon atoms accelerate developing rates and energize weak developers. While such compounds when present in developing solutions decrease the developing time, their full efficiency can not be utilized because of their limited solubility in alkaline developer solutions. Moreover, they are characterized by unpleasant odors, which tend to discourage their commercial use.

It is, therefore, an object of the present invention to provide a black and white and color deso that the developing time is decreased by less than one-half of the normal time without loss of speed and contrast.

Another object of the present invention is to veloper having an increased rate of development 1 provide a delevoper which is not only less toxic than those heretofore used, but also characterized 1 by a very pleasant odor.

Other objects and advantages will appear hereinafter.

722, 2,292,575, 2,303,928, and 2,30'7399, with a color developer containin an alkyl ether of a polyhydroxyaralkylamine, the developing time is cut from 20-30 minutes to 2-10 minutes All of 1" Application November 16, 1949, Serial No. 127,780

2 the layers are simultaneously developed and the dye images formed are of excellent quality.

The developing time with black and white developers, for instance, solutions of hydroquinone and Metol (p-methylaminophenol sulfate) and the like, is also cut by more than half without causing fog when such solutions contain an alkyl ether of a polyhydroxyaralkylamine.

The alkyl ethers of polyhydroxyaralkylamines employed in accordance with the present invention are characterized by the following general formulae:

and

. s em group, and n represents a positive integer of from 1 to 2, R3 isonly methyl. when .n is 1 and R4 is only methyl when R3 is hydrogen.

The following are illustrative examples of such alkyl ethers of polyhydroxyaralkylaminesz unionism B-(3.4-dimethoxyphenyl)ethylamim 4 Ber. 42, 1986. v v

" Emma con} 4 x W 3,4-dimethoxybenzylamine Ber. 41, 18. v

CH2.NH:

l QOCH:

4-hydroxy-3-methoxybenzylamine J. A. C. S. 41, 1118.

. J 5*- (ehydroxyes-methoxyphenynethylamine Beilstein, 151; Supplement XIII, 324.

3.methylenedloxybenzylamine Ber. 45, 318.

CH. ('JH-NH:

@OCH:

a-(4-hydroxy-3-methoxyphenyl)ethylamine .f. c. s. 99, 417.

H Q CH3 CH (3,4-filmethoxypheny1) propylamine Ber. 43. 193.

cmcmNH Q0 CzHi Ca s B- (3,4-diethoxypheiiyl) ethylamlne Arch. Pharm. 272 60 (C. A. 28, 3412).

CH3CH2.NE2

sCzOQb C2 5 0 0 :H5 B- 3,4.5-triethoxyphenyl) ethylamine J. Prakt. Chem. 137, 339.

O C H;

G 2H5 I? (3H1]ethairy-feethoxyphenyl) ethylamine CH2.CHg.NHz

-CH; B- (3,4-methylenedioxyphenyl) ethylamine Beilstein, 1st Supple. )HX, 766. Ber. 43, 3414.

' ("Hg.CHz.NE 3

CH; v'18- 3.4;5-trimethoxyphenyl) e't'hy'l'amine Monatshefte 40, 145.

3A,5-ttimethoxybenzylamine Zer. 38, 3639.

These alkyl ethers of polyhyd'roxyaralkylamines are soluble in water and in alkaline developers and may be used in specified amounts. Their solubility in water and in alkaline developers can be made appreciable by converting'tlie base into a salt, such as, for example, the sulfate, hydrochloride, carbonate, or carbamate.

lgraphic layers containing .oiolor formers rast to difiusion with a color developer containing an 'alkyl ether of a polyhydroxyaralkylamine, the developing time is cut from20-30 minutes to 2:12

minutes. All of the layers are simultaneously developed, and the dye images formed are of excellent quality.

The developing time with black and whitedevelopers, for instance, solutions of hydroquinone and monomethylaminephenol sulfate and the like, is also cut to one-half without causing :fog

. when such solutions contain an alkyl ether of a polyhydroxyaralkylamine.

As illustrative of developing solutions containing such alkyl ethers of polyhydroxyaralkylamines; thefollowing arefgiven:

The foregoing developer on five minutes development at 20 C. of the usual black and white roll film gives a negative of good density and gradation after fixing and washing. The time required to develop an identical film in a similar solution but containing no 4-hydroxy-3-methoxybenzylamine ranges from to minutes.

The foregoing developing olutions containing the 4-hydroxy-3-methoxybenzylamine develops up to 1 -2 stops more speed in about 14 minutes as compared to the same developing solution containing no 4-hydroxy-3-methoxybenzylamine.

Example II The following developer requires minutes at 20 C. to give a satisfactory degree of color de- By the addition of 4 grams of B-(3A-dimeth- 'oxyphenyl) ethylamine to the foregoing solution,

a color paper of excellent color rendition is developed in about 12 minutes with a higher shoulder density and improved contrast. Without the presence of said amine at least 30 minutes is required to give an acceptable print. Increasing the concentration of the amine further reduces the time of development.

The color photographic multilayer element utilized in the foregoing example consists of an integral tri-pack emulsion coated on either the usual paper base, or a clear cellulose acetate or nitrate film base, or in some cases an opaque white film base. Each of the emulsion layers is sensitized to one of the primary colors of light, namely, blue, green, and red. The top layer is blue sensitive. A filter layer, yellow in color and blue absorbing, lies under the top layer. Below this filter layer lies a green sensitive emulsion layer, and below this a red sensitive emulsion layer. Each of the three silver halide emulsion layers contains dye forming compounds which unite during the development of a silver image in an aromatic amine developing agent to form a dye with the oxidation product of the developing agent. As silver is also formed during development, it must be removed after color development by treatment in a bleach, followed by a .bath of sodium thiosulfate, as is well known in the art. A yellow dye is formed in the blue sensitive emulsion; a magenta dye is formed in the green sensitive emulsion; and a cyan dye is formed in the red sensitive emulsion. The combination of the dye images from these three printing primaries yields the color picture. Suit- 6. able methods for the preparation of multicolor emulsion layers have been described in the literature relating to color photography, and are, therefore, not described here.

Errample III Example II was repeated with the exception that 8 grams of the p-amino-di(p hydroxyethyl) aniline sulfate were replaced by 6.9 grams of p aminoethylqi hydroxyethyl) aniline sulfate. The development of the same color paper was reduced from 25-30 minutes at 70 F. to 8 minutes at the same temperature.

,7 Example IV Sodium hexametaphosphate grams 1.0 Sodium sulfite do 4.0 4-amino-ethyl s-hydroxyethyl) aniline sulfate ".d0 5.0-.

Sodium carbonate (monohydrate) do 50.0 Potassium bromide do 1.0 Water to make liters 1 The addition of 4 grams of 3,4-methylenedioxybenzylamine to the foregoing developing solution reduces the developing time of a multicolor film of the reversal type containing color formers fast to diffusion by 50% and in addition gave an increased shoulder density and improved contrast.

Example V Example I was repeated with the exception that 4 grams of 4-hydroxy-3-methoxybenzyl amine were replaced by 5 grams of 3,4,5-trimethoxy-p-phenylethylamine. The results were identical with those obtained in Example I.

The above examples are to be regarded as merely illustrative of the invention and not. in any sense restrictive. It will be obvious to those skilled in the art that many modifications, such as substituting equivalent materials and varying the proportions of the materials used, are within the spirit and scope of the invention. The scope, therefore, of the invention is to be limited solely by the following claims.

I claim:

1. An alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent and an alkyl ether of a polyhydroxyaralkylarnine selected from the class consisting of those of the following formulae:

and

( 0 H2) n N I -CH: wherein R is selected from the class consisting of methyl and ethyl, R1 is selected from the class consisting of hydrogen, methyl and ethyl, R2 is selected from the class consisting of hydrogen, methoxy and ethoxy, R3 and R4 are selected from the class consisting of hydrogen and. methyl, and

.11, iissa; positive integer of from .1 :to :2, R3 is only methyl when n is ,1, and :is only methyl when R; is hydrogen, and thesalts'of said amines.

2. An alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent and l-hydroxy- 3-methoxybenzylamine.

:3. An alkaline photographic developer for silver :halide emulsions comprising an aromatic silver halide developing agent and ,18-(3A-di- .methoxyphenyl) ethylamine.

4.:An alkaline photographic developer vfor silver halide emulsions comprising an aromatic silver halide developing agent and ISA-methylenedioxybenzylamine.

I *5. In the processing ofphotographic'material,

the improvementwhich comprises developing an exposed silver halide emulsion in an alkaline .devloper .containing .an aromatic silver. halide developing agent and a developing accelerator consisting of an alkyl ether of a polyhydroxyaralkylamine selected from the class consisting of those of the followingformulae:

' his wherein R is selected from the class consisting of methyl and ethyl, R1 is selected from the class .consisting of hydrogen, methyl and ethyl, R2 is selected from the class consisting of hydrogen, methoxy and ethoxy, Rsand R4 are selected from the class consisting of hydrogen and methyl, and his a positive integer of from 1 to 2, R3 is only methyl when n is 1, and R4 is only methyl when R3. is hydrogen, and the salts of said amines.

6. In the processing of photographic material, the improvement which comprises developing an exposed silver halide emulsion in an alkaline developer containing an aromatic silver halide developing agent and a developing accelerator consisting of "4-hydroxy-3-methoxybenzylamine.

7. In the processing of photographic material,

8 the improvement which comprises developing an exposed silver halide emulsion in an alkaline developer'containing an aromatic silver halide developing agent and a developing accelerator consisting of .13 (3,4 dimethoxyphenyb'ethylamine.

8. In the processing of photographic material, the improvement which comprises developing an exposed silver halide emulsion in .an alkaline developer containing an aromatic silver halide developing agent and a developing accelerator consisting of 3,4-methylenedioxybenzylamine.

9. .A color forming photographic developer comprising a primary aromatic amino developing agent and an .alkyl ether of a polyhydro'xyaralkylamine selected from the class consisting of those of the following formulae: L

and

c in) ,.NH,

O-CH2 wherein R is selected from the class consistin of methyl and ethyl, R1 is selected from the class consisting of hydrogen, methyl, and ethylyRz is selected from the class consisting of hydrogen, methoxy and ethoxy, R3 and R4 are selecte'cl'from the class consisting of hydrogen and methyl, and n is a positive integer of from. 1 to 2, R3 is only methyl when n is l, and R4 is only methyl when R3 is hydrogen, and the salts of said amines.

10. A color forming photographic developer comprising a primary aromatic amino developing agent and 4-hydroxy-3-methoxy benzylamine.

11. A color forming photographic developer comprising a primary aromatic amino developing agent and B-(SA-dimethoxyphenyl)ethylamine.

1 A color forming photographic developer comprising a primary aromatic amino developing agent and 3,4-methylenedioxy-benzylamine.

IVY V. RUNYAN.

No references cited.

Claims (1)

1. AN ALKALINE PHOTOGRAPHIC DEVELOPER FOR SILVER HALIDE EMULSIONS COMPRISING AN AROMATIC SILVER HALIDE DEVELOPING AGENT AND AN ALKYL ETHER OF A POLYHYDROXYARALKYLAMINE SELECTED FROM THE CLASS CONSISTING OF THOSE OF THE FOLLOWING FORMULAE: