US3615525A

US3615525A - Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition

Info

Publication number: US3615525A
Application number: US727358A
Authority: US
Inventors: Jozef Frans Willems; George Frans Van Veelen
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1967-05-24
Filing date: 1968-05-07
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: DE1772490A1; NL6807365A; GB1191535A; BE715500A

Abstract

Photographic developing compositions comprising hydroquinone and a quinoline derivative having the formula

WHEREIN R1 is an alkyl group comprising from one to five carbons atoms, R2 is an alkyl group comprising from one to five carbon atoms, and R3 is hydrogen, or an alkyl group comprising from one to five carbon atoms, at most one of R1, R2 and R3 being substituted alkyl are described. These compositions provide super-additive development in photographic processes.

Description

United States Patent [72] Inventors Jozef Frans Willems Wilrljk; George Frans Van Veelen, Mortsel, both of Belgium [2i] Appl. No. 727,358

[22] Filed May 7, 1968 [45] Patented Oct. 26, 1971 [73 1 Assignee Gevaert-AGFANV Mortsel, Belgium [32] Priority May 24, 1967 [33] Great Britain [54] DERIVATIVE OF 6-AMINO- l,2,3,4- TETRAI-IYDROQUINOLINE AS SUPERADDITIVE IN DEVELOPING COMPOSITION 8/1966 Willems et al.

OTHER REFERENCES Willems, et al. (ll): Photographic Science and Engineering, Vol. 10, pages 306- 313(1966) Primary E.raminer-Norman G. Torchin Assistant Examiner- Won H. Louie, Jr. Attorney-Alfred W. Breiner ABSTRACT: Photographic developing compositions comprising hydroquinone and a quinoline derivative having the formula wherein R is an alkyl group comprising from one to five carbons atoms. R. is an alkyl group comprising from one to five carbon atoms, and R is hydrogen, or an alkyl group comprising from one to five carbon atoms, at most one of R,, R and R being substituted alkyl are described. These compositions provide super-additive development in photographic processes.

DERIVATIVE OF 6-AMINO- 1 ,2,3,4- TETRAHYDROQUINOLINE AS SUPERADDITIVE IN DEVELOPING COMPOSITION The invention relates to a process for the development of photographic materials, Containing exposed silver halide, and to developing compositions used therein.

It is known that the developing activity of a developing solution contains a mixture of several developing substances can be higher than the sum of the developing activities of the separate developing solutions of each of these developing substances used in the same concentration as in the solution of that mixture. This phenomenon is called the superadditive development.

The most common example of superadditive development is that of the combination of p-monomethylaminophenol hemisulfate and hydroquinone, which has been described by G. Pizzighelli, Lietfaden der prakrischen Photographic, Auflage l4(Pau1Nanneke)p. 177.

It is further known from British Pat. specification No. $42,502 that the combination of hydroquinone and l-phenyl- 3-pyrazolinone has a more intense developing action than the combination of hydroquinone and pmonomethylaminophenol hemisulfate.

In our British Pat. specification No. 989,383 it has been described that developing baths with a mixture of hydroquinone and particular p-phenylene diamine derivatives selected from N,N'-tetraalky1-p-phenylene diamines of which one of the alkyl groups may be substituted by water-solubilizing groups such as hydroxyl and sulfo, 6-amino-l,2,3,4- tetrahydroquinoline and 6-amino-l-alkyl-tetrahydroquinolines have a higher developing activity than the combination of hydroquinone and p-monomethylaminophenol hemisulfate and show the advantage over the combination of hydroquinone and l-phenyl-3-pyrazolidinone of being stable to hydrolysis even in strong alkaline medium.

It has now been found that an exceptional superadditive developing activity is obtained when using, in the development of exposed silver halide emulsion layers, a combination of developing agents consisting of hydroquinone and a com pound corresponding to the general formula:

R1 (IDH on, \C/

wherein R stands for lower alkyl comprising from one to five carbon atoms,

R, stands for lower alkyl comprising from one to five carbon atoms including substituted lower alkyl e.g. hydroxyalkyl, carboxyalkyl, the group R-NHSO R wherein each of R and R stands for lower alkyl, the group XSO; M wherein X stands for a straight chain or branched alkylene radical having from two to five carbon atoms in straight line and M stands for hydrogen, an alkali metal atom such as sodium or potassium, ammonium or an amine and R stands for hydrogen, lower alkyl comprising from one to live carbon atoms including substituted lower alkyl e.g. alkyl substituted as exemplified for R at most one of R and R being substituted alkyl.

The combinations of developing agents according to the invention show as compared with the developing combinations described in our British Pat. specification No. 989,383 a markedly higher development activity. In most cases they even have a higher activity than the developing combination of hydroquinone and 1-phenyl-3-pyrazolidinone. Moreover, the developing compositions of the invention have the further advantage of being stable to hydrolysis, even in strong alkaline medium whereas compositions with l-phenyl-3- pyrazolidinone hydrolyse in strong alkaline baths. Thus with the developing combinations of the invention very stable developing solutions are obtained which is pahticularly interesting for preparing liquid developers.

The compounds corresponding to the above general formula can be added to the developing bath in the form of free bases as well as in the form of their salts e.g. as hydrochloride, as sulfate, etc.

The following are examples of compounds corresponding to the above general formula:

1. o-diethylaminol ,2,3,4-tetrahydroquinoline dihydrochloride; 2. l-ethyl-6-diethylamino-1,2,3 ,4-tetrahydroquinoline 7. l-( 2-methylsulfonylamino-ethyl )-6-diethylaminol,2,3,4-tetrahydroquinoline dihydrochloride; 8. 1-( 3-carboxypropyl)-6-dimethylamini-l ,2,3,4-

tetrahydroquinalone.

The 6-aminc-tetrahydroquinoline derivatives of use according to the present invention can be prepared by alkylation of 6-amino-tetrahydroquinolines or by alkylation of 6-dialkylamino-tetrahydroquinolines. The 6-dialkylaminotetrahydroquinolines are prepared by hydrogenation of the 6- dialkylaminoquinolines, which in their turn can be prepared as described in Bull. Soc. Chim. Fr. 27 1920) 430.

The following preparations illustrate more particularly how the 6amino-tetrahydroquinoline derivatives of use according to the invention can be prepared.

Preparation 1:.Compound l A solution of g. (0.4 mole) of o-diethylamino-quinoline in 400 ml. of anhydrous ethanol is hydrogenated, using 8 ml. of Raney nickel as catalyst, in a sealed tube at 70 C. and a hydrogen pressure of 1,500 p.s.i. The uptake of hydrogen is complete after min. The catalyst is filtered ofi and the filtrate is treated with 200 ml. of concentrated hydrochloric acid. After evaporation of the alcohol the residue is recrystallized from a mixture of ethanol and ethyl acetate. Melting point: C.

Preparation 2: Compound 2 40.4 g. (0.2 mole) of 6-diethylamino-l,2,3,4- tetrahydroquinoline and 18.2 g. (0.1 mole) of triethylphosphate are heated for 3 hours in an oil bath at 200 C. After having been cooled to 50 C. a solution of 15 g. of sodium hydroxide in 50 ml. of water is added and heating is continued for 90 min. The reaction mixture is treated with water and extracted with ether. After evaporation of the ether the residue is distilled. The l-ethyl-6diethylamino-l,2,3,4- tetrahydroquinoline has a boiling point of 184-l87 C./14 mm. It is converted into its dihydrochloride by treating the base, dissolved in ethanol, with alcoholic hydrochloric acid. Melting point: 172 C. (after recrystallization from a mixture of ethanol and ethyl acetate).

Preparation 3 Compound 3 80.8 g. (0.4 mole) of 6-diethylamino-l,2,3,4- tetrahydroquinoline and 54.4 g. (0.4 mole) of butane sultone are heated for 3% hours, in an oil bath at C. The reaction mixture is dissolved in 750 ml. of water and treated with 16 g. (0.4 mole) of sodium hydroxide dissolved in 75 ml. of water. The aqueous layer is extracted three times with ether. Then the aqueous layer is treated with 160 ml. of 2.5N hydrochloric acid and evaporated. The residue is boiled with 500 ml. of anhydrous ethanol. The undissolved sodium chloride is filtered off and the ethanol filtrate is evaporated. The product is dried bisulfites, metabisulfites, sultites, and acids such as boric acid and citric acid. The developing bath may further contain potassium bromide, water-softening agents such as polyphosphates or derivatives of ethylene diamine tetraacetic acid, antifogging agents and moistening agents, as well as other compounds known in the developing technique.

The pH of the baths can vary within wide limits, preferably between eight and 1 1, so that a rapid or slow development can be obtained at will resulting in high-contrast and low-contrast images respectively.

The ratio of hydroquinone to a G-amino-tetrahydroquinoline derivative used in the present invention, can be chosen in such a way that the bath composition is suited for the development of all kinds of materials including materials having silver chloride emulsion layers of low sensitivity as well as materials having sensitive silver bromoiodide emulsion layers.

The ratio of hydroquinone to the 6-amino-tetrahydroquinoline derivatives used in the present invention can vary within wide limits. The amounts are, however, generally chosen in such a way that the hydroquinone strongly outweighs the said derivatives. A strong superadditive effect is already obtained with a ratio of 50 mg. of a said derivative used in this invention to 5 g. of hydroquinone per liter. Generally the amount of hydroquinone is comprised between 1 and 30 g. per litre and the amount of 6-amino-tethydroquinoline derivative between 5 mg. and 2 g. per liter.

Combinations of developing agents used in this invention may also be applied in the treating solution and/or in the lightsensitive material and/or in the image-receiving material used in the application of the silver complex diffusion transfer process, the principle of which is described in British Pat. specification Nos. 614,155 and 654,630 and in German Pat. specification No. 887,733. For more details concerning the silver complex diffusion transfer process, the different embodiments of the materials and apparatus used therein, there can be referred to Progress in Photography 1955-1958, p. 24-36 and the patent literature cited therein.

The following examples illustrate the present invention.

Example 1 Strips of a photographic material comprising a light'sensitive silver bromoiodide emulsion layer, coated on material comprising triacetate support, are exposed through a grey filter with light-quantity (E) which corresponds to the shoulder part ofthe density/log E curve.

One of these film strips is developed in a bath A having the following composition:

sodium carbonate sodium hexametaphosphate 1.0 g. sodium sulfite "0.0 g. potassium bromide 0.5 g. hydroquinone 4.4 8. water up to 1.000 ml.

The other strips are developed in baths having the same composition as bath A but moreover containing an equivalent amount of a developing agent as listed in table 1 given hereinafter.

The results of these developing tests are listed in table 1. The densities are determined after a development time of 30, 6060 and 90 sec.

propyl-p-phenylene diamine From these results it clearly appears that the developing combination of the invention has a higher activity than the developing combinations of our British Pat. specification No. 989,383.

Example 2 5 ing the following composition:

boric acid 5.0 g. borax I0.0 g. sodium hexametaphosphate 1.0 g. sodium sulfite 20.0 g. potassium bromide 0.5 g. hydroquinone 4.4 g.

water LIP [O The other strips are developed in developing baths having the same composition as bath B, but containing moreover an equivalent amount of a developing agent as listed in table 2 given hereinafter.

The densities are determined after 1, 3 and 5 respectively Table 2 Developing bath Density after a developing time of l min. 3 min. 5 min bath 8 0.04 0.04 0.04 bath B+ mg. of compound 1 0.20 1.20 1.60 bath B+ mg. of compound 2 0.80 1.45 1.70 bath B+l05 mg. of compound 3 0.05 0.84 1.25 bath B+70 mg. of l-methyl-oamino-l,Z.3,4-tetruhydroquinoline oxalate 0.05 0.46 1.00 bath B+l07 mg. of N.N-diethyl-N- propyl-N-3-sulphopropyl-p-phenylene diamine 0.05 0.17 0.58 bath B+50 mg. of l-phenyl-3- pyrazolidinone 0.05 0.46 1.10

From these results it appears that the developing activity of the combination of developing agents according to the invention is not only higher than that of the developing combinations of our British Pat. specification No. 989,383 but even higher than that of the combination of 1-phenyl-3- pyrazolidinone and hydroquinone.

Example 3 Strips of a photographic material comprising a silver bromoiodide emulsion layer were exposed through a step wedge and developed for 2 minutes in a developing bath C having the following composition:

sodium carbonate 20.0 g. sodium sulfite 20.0 g. potassium bromide 10 g. hydroquinone 4.5 g. water up to 1.000 ml.

Other strips were developed in baths having the same composition as bath C but moreover containing an equivalent amount of a developing agent as listed in table 3, hereinafter. These baths were used either directly after their preparation or after having been stored for some time in closed containers at 80 c. The results of the developing tests before and after storage are listed in table 3.

From these results it appears, that compound 3 is much more stable against hydrolysis than l-phenyl-3-pyrazolidiuone and for this reason is interesting for preparing liquid developers.

What we claim is:

I l. Photographic developing composition comprising hydroquinone and a derivative of 6-amino-l,2,3,4- tetrahydroquinoline corresponding to the following general formula, in the form of the free base or in its salt form 3 R1 ?H2 \N CH: 0 R2 Hz wherein R is an alkyl group comprising from one to five carbon atoms.

R is an alkyl group comprising from one to five carbon atoms, and

R is hydrogen, or an alkyl group comprising from one to five carbon atoms,

at most one of R R and R being substituted alkyl.

2. Photographic developing composition according to claim 1, wherein one of R,, R and R is a hydroxyalkyl group, a carboxyalkyl group, or the group R-NHSO R wherein each of R and R is a lower alkyl group, the group -X-SO M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.

3. Photographic developing composition according to claim 1, wherein each of R and R is a lower alkyl group having from one to five carbon atoms, and R is hydrogen, a lower alkyl group having from one to five carbon atoms or the group -X-SO M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.

4. Photographic-developing composition according to any of claim 1, wherein the said hydroquinone is present in an amount of from 1 to 30 g. per litre and the said 6-aminol,2,3,4-tetrahydroquinoline derivative in an amount offrom 5 mg. to 2 g. per litre.

5. Photographic-developing method comprising developing and exposed silver halide emulsion layer of a photographic material an means of hydroquinone and a 6- aminol,2,3,4tetrahydroquinoline derivative as defined in claim 1.

6. Photographic-developing method according to claim 5, for application in the silver complex diffusion transfer process wherein the exposed light-sensitive material is developed with an aqueous alkaline solution in the presence of hydroquinone and a o-amino-l,2,3,4-tetrahydroquinoline derivative as defined in claim 1.

UNITED STATES PATENT OFFICE i ifIERTIFICATE OF CORRECTION Patent No 3, 615, 52 5 Dated October 26, 1817] imentorfs) JOZEF FRANS WILLEMS ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Title page under References Cited, United States Patents, 727, 358" should read 3, 265, 502 Column 1, line 9, "contains" should read containing Column 2, line 17 (NO. 5), (N-ethyl-nN-3--suli'o1oropylg amino)" should read (N-ethyl-N-S-sulphopropyl-amino)- 7 Column 2, lines 24 25 (No. 8), "6dimethylamini-1, 2, 3,4-tetrahydrot tinalone" should read 6-dimethylamino- 1, 2, 3, 4-tetrahydroouinoline Column 3, line 16, after "having insert highly Column 3, lines 43 44, "material comprising" should read a ceiulose Column 3, line 45, after "with" insert a Column 3, line 61, "6060" should read 6O Column 4, line 28, after "5" inser min. Column 6, lines 20 21, claim 4, after "according to dei te any of Column 6, line 26, claim 5, "and" should read an Column 6, line 27, claim 5, "an" should read by Column 6, line 28, amino 1, 2, 3, 4tetrahydroquinoline" should read amino- 1, 2, 3, 4-tetrahydroquinoline Signed and sealed this 16th day of December 1973.

(SEAL) Attest:

EDlJARD M. FLETCHER, JR. RENE D. TEGTliEZ'ER Attesting; Officer Acting Commissioner of Patents RM F'O-WULO r10-69) USCOMM oc 6037B P59 U 5 GOVERNMENT PRINTING OFFICE 1969 D-36i33l,

Claims

2. Photographic developing composition according to claim 1, wherein one of R1, R2 and R3 is a hydroxyalkyl group, a carboxyalkyl group, or the group -R-NHSO2R4 wherein each of R and R4 is a lower alkyl group, the group -X-SO3M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.
3. Photographic developing composition according to claim 1, wherein each of R1 and R2 is a lower alkyl group having from one to five carbon atoms, and R3 is hydrogen, a lower alkyl group having from one to five carbon atoms or the group -X-SO3M wherein X is a straight or branched alkylene group having from two to five carbon atoms in straight line, and M is hydrogen, an alkali metal, ammonium or an amine.
4. Photographic-developing composition according to any of claim 1, wherein the said hydroquinone is present in an amount of from 1 to 30 g. per litre and the said 6-amino-1,2,3,4-tetrahydroquinoline derivative in an amount of from 5 mg. to 2 g. per litre.
5. Photographic-developing method comprising developing and exposed silver halide emulsion layer of a photographic material by means of hydroquinone and a 6-amino-1,2,3,4-tetrahydroquinoline derivative as defined in claim 1.
6. Photographic-developing method according to claim 5, for application in the silver complex diffusion transfer process wherein the exposed light-sensitive material is developed with an aqueous alkaline solution in the presence of hydroqUinone and a 6-amino-1,2,3,4-tetrahydroquinoline derivative as defined in claim 1.