US3346386A - Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants - Google Patents
Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants Download PDFInfo
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- US3346386A US3346386A US329364A US32936463A US3346386A US 3346386 A US3346386 A US 3346386A US 329364 A US329364 A US 329364A US 32936463 A US32936463 A US 32936463A US 3346386 A US3346386 A US 3346386A
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- Prior art keywords
- phosphoric acid
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- compound
- adjuvants
- silver halide
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Classifications
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- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
- G03C5/3056—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3356—Polymers modified by chemical after-treatment with organic compounds containing phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/15—Lithographic emulsion
Definitions
- the invention relates, to a process for the production of photographic images, the development of the exposed photographic material being carried out in the presence of polycondensation products of phosphoric acid amide derivatives with aliphatic polyethers.
- Phototechnical films of the co called lithoor line-type are increasingly being used in the reprography, in particular photo production of screened photographic prints.
- Lithoor line films. are such films which can be developed in developer c0mpositions containing formaldehyde bisulfite compounds to very high 'y-values and thus to sharp screened dots.
- the term 'y is to be understood the tangent of the angle between the straight-line portion of the characteristic curve (or H and D curve) of the leg E axis.
- a further object is to provide compounds which simultaneously effect the development in such a manner that the period of time during which that high *y-value is obtained can be extended so that the development is more convenient and simpler.
- R represents an alkyl group preferably with up to 5 carbon atoms or an aryl, preferably phenyl or alkyl phenyl, or aralkyl, such as benzyl group
- R can have the same meaning as R or can represent a hydrogen atom
- X represents halogen atoms such as bromine or preferably chlorine, or alkoxy groups, preferably short-chain groups having up to 5 carbon atoms such as methoxy and ethoxy
- R and R can be together the methylene groups to form a heterocyclic rin in particular a piperidine or pyrrolidine ring.
- polyethers are polyethylenglycols which contain at least 3, preferably 410 CH CH .O- units.
- polyether are advantageously reacted with, 1 mol Qf theamido phosphoric acid compound.
- lithe development or litho developer we intend a development process which yields images with very steep gradation of at least 3 by the use of a developer which contains a formaldehyde-bisulfite compound.
- Suitable for the process according to the invention are all silver halide emulsions which show a sufiiciently high gradation effect with developers which contain formaldehyde.
- the silver salts in such least 50 mol percent of according sions, the
- ernnl-t silver halide of which contains at least 65 mol percent of silver chloride and 35 mol percent or less silver in the emulsion. It is advantageous to use from 10 to 100' mg. per mol of silver halide.
- the compounds are added to the developer solutions or to the emulsions, advantageously in quantities of 30 to 300 mg./ liter of the emulsion-casting solution.
- the final dried silver halide emulsion layer with such addition accordingly contains between 0.5 and 10 mgrof the compound per squarc meter.
- the ry-value in the development is shifted from about 6 to 8 to 15; Moreover, the period of development time during which the steepest gradation or screen dot sharpness is produced is raised from about 1 minute to 3 to 4 minutes.
- An additional advantage is that a developer containing formaldehyde is much less dependent'upon temperature when it has such an additive. Whereas a developer *without this additive reacts with a considerable development acceleration and thus a pronounced shortening of the development time when the temperature is raised by 1 to 2, good results are obtained with a developer temperature between 15 and 40 when phosphoric acid amide esters are added. Because of the longer processing period, the advantages described above lead to much more reliable Working.
- the compounds according to the invention can be'added to the developer composition in an amount of 0.01 to 10 grams per liter of the aqueous composition.
- the phosphoric acid amide esters according to the invention are prepared by conventional esterification methods; the degree of condensation of the ester can be influenced as required by variations in the reaction time and in the reaction temperature. The higher the temperature, the higher is the. degree of condensation of the phosphoric acid amide esters, in particular the integer'Z" of the polyether ester formula can be influenced by varying the temperature. Thus, compounds were obtained in which Z had a value of about 100, 300, 800 or 1000. The degree' of condensation can further. be influenced, in particular the integer ,Z referred to hereinbefore, by varying the proportion of the starting compounds for theconden'sation.
- COMPOUND II 41.2 g. of nonaethylene glycol, 31.2 g. of pyridine and 19g. of N,N-diethyl phosphoric acid amidedichloride are reacted and worked up in the manner described above.
- COMPOUND IV 41.4 g. of nonaethylene glycol, 31.2 'g. of pyridine and 22.4 g. of N-methyl-N-phenyl phosphoric acid amidedichloride are reacted in a manner analogous to Compound 'I. There are formed 50 g. of'a brown-coloured semi-solid substance, which is diluted with water and decolourised with activated carbon.
- ethylene glycol in the presence of'reesterification catalysts, such as sodium or sodium'alcoholate, for several hours at 100 to 120 C.
- the ethyl alcohol that is liberated is constantly distilled 01? in vacuo and the residue can be used I for the purpose of the present invention.
- Example 1 A'gelatino-silver halide emulsion with 15 mol percent of AgBr and of AgCl is washed, ripened to the maximum sensitivity and, after adding 4-hydroxy-6-methyl- 1,3,3a,7-tetrazaindol or other stabilisers and a Wetting agent, cast onto a suitable film support; 7
- film strips are prepared with the use of the same emulsions, 80 mg. of octaethylene glycol or 80 mg. of the Made up with water to 1 litre.
- Example 2 Film strips of the emulsion described in'Example 1 are exposed behind a grey stepped wedge and are developed in the developer referred to above for periods from 1 to 6 minutes (Experiment A). The same film specimens, after addition of mg. of the Compound I (Experiment B) and 100 mg. of the phosphorous acid glycol ester according to Example 1 of Belgian Patent 609,497 (Experiment C), are developed in the same developer. 1
- Example 3 An emulsion as in Example 1 is given the usual additives (wetting agents, stabilisers and hardeners) and is divided into three portions and cast as follows onto a film support:
- reaction products has the following formula:
- R1 R2 Z wherein R and R have the meaning defined in claim 1, m can be 0 and an integer from 3 to 10; n is an integer from 3 to 10 and Z is an integer from 1 to 1000.
- reaction product has the following formula 1
- An aqueous composition containing a silver halide photographic developer and from 0.01 to 10 grams per liter of a compound of the following formula:
- m can be 0 and an integer from 3 to 10; n is an integer from 3 to 10 and Z is an integer from 1 to 1000.
Description
United States Patent 3,346,386 POLYCONDENSATION PRODUCTS 01? PHOS- PHORIC ACID AMIDES WITH ALlPHATIC POLYETHERS AS DEVELOPER ADJUVANTS Herbert Miiller, Leverkusen, HerbertGrabhijfer, Cologne- Flittard, Hans Ulricli, Leverkusen, and Rolf-Fred Posse, Cologne-Flittard, Germany, assignors to Agfa Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Dec. 10, 1963, Ser. No. 329,364 Claims priority, application Germany, Dec. 17, 1962,
A 41,899 Claims. (Cl. 96-66.3)
The invention relates, to a process for the production of photographic images, the development of the exposed photographic material being carried out in the presence of polycondensation products of phosphoric acid amide derivatives with aliphatic polyethers. Phototechnical films of the co called lithoor line-type are increasingly being used in the reprography, in particular photo production of screened photographic prints. Lithoor line films. are such films which can be developed in developer c0mpositions containing formaldehyde bisulfite compounds to very high 'y-values and thus to sharp screened dots. The term 'y is to be understood the tangent of the angle between the straight-line portion of the characteristic curve (or H and D curve) of the leg E axis.
It is true that processing of such films with formaldehyde-containing developers leads to excellent results, but the operation must be performed with great care, since the period during the development which yields a sharp screen dot, i.e., steepest gradation, is too brief, approximately between half and 1 /2 minutes.
It is known to add phosphorylated alkylene oxide derivatives to photographic silver halide emulsions to improve the mechanical properties. Such compounds are,
however, not operative for producing a steep gradation.
It is an object of the present invention to provide novel compounds Which are added to the photographic layers or to the aqueous developing composition and with which an extremely high v-value can be obtained upon development. A further object is to provide compounds which simultaneously effect the development in such a manner that the period of time during which that high *y-value is obtained can be extended so that the development is more convenient and simpler. Other objects, some of which are referred to specifically hereinafter will be. evident to those skilled in the art to which this invention pertains.
These objects have been achieved by providing condensation products of aliphatic polyethers with terminal hydroxy groups and phosphoric acid amide derivatives of the formula in which R represents an alkyl group preferably with up to 5 carbon atoms or an aryl, preferably phenyl or alkyl phenyl, or aralkyl, such as benzyl group; R can have the same meaning as R or can represent a hydrogen atom and X represents halogen atoms such as bromine or preferably chlorine, or alkoxy groups, preferably short-chain groups having up to 5 carbon atoms such as methoxy and ethoxy; R and R can be together the methylene groups to form a heterocyclic rin in particular a piperidine or pyrrolidine ring.
Especially suitable polyethers are polyethylenglycols which contain at least 3, preferably 410 CH CH .O- units.
3,346,386 Pa ented s 0, 1.86.7
To pr d ce e de sa io pr d cts, 2 ENE: of.
polyether are advantageously reacted with, 1 mol Qf theamido phosphoric acid compound. The following amide p sp o ic d omp ds i pa i u a u li CH NHPOCI C H NHPOCl C H NH-POCI C H NHPOCl s s iP 12 4-ClC H NHPOCl 2-,4'-Cl;C H N'HPOCl & a)a s '2NH C 2 CH NPOCI 0 1a, ,NPocr (CgHgJgNPOBI'z lSO-C4H9) a n sNPOC i (Cs 5) 2 5 PQC z 6 5)2 C 2 5H10 C 2 I cnannrow i oi 2H5 H C2H5J2 CSH'LNHPO(OC2H5)V2 $Q'-C4H9 H 2 5)2 C6H5NHPO(OCH3)2 sH5 .HP (Q 2 5)2 CsHsNHPO( CsH'i-is9.)2 2.,4-CI CGH3NHP to nail -Q aCs 4 H (Q 2H5)-a H3)2 (OC T )2 2 s)2NP (-Q Ha). a '1)2NP gH5)a (C4 9).2 Q( C4 9.) 2- (Cs s) z P' z sh The aforesaid compounds are described, for example, in the article by A. Michaelis, Ann. volume 326, 129 1903 The products which are obtained by reaction of the above components and which are generally water-soluble, probably have the following structure:
HO lCHz-QHz-O) the integers n, m and Z have the following meaning;
m=0 or at least 3, preferably 4-10; n=at least 3, preferably 4--10; .=l t: s 1, pre e ab y .400
The action of these compounds in connection with lithe development was all the more unexpected because shortchain polyethylene glycols such as octaethylene glycol and even the analogous phosphoric and phosphorous acid polyethylenglycol ester, as described in Belgian Patent 609,497, do not produce any sharp gradations. By the term lithe development or litho developer we intend a development process which yields images with very steep gradation of at least 3 by the use of a developer which contains a formaldehyde-bisulfite compound.
Suitable for the process according to the invention are all silver halide emulsions which show a sufiiciently high gradation effect with developers which contain formaldehyde.
The silver salts in such least 50 mol percent of according sions, the
emulsions ge e av com rise at i e ch or de Pe the pros s to the invention, it is preferred to use ernnl-t silver halide of which contains at least 65 mol percent of silver chloride and 35 mol percent or less silver in the emulsion. It is advantageous to use from 10 to 100' mg. per mol of silver halide. The compounds are added to the developer solutions or to the emulsions, advantageously in quantities of 30 to 300 mg./ liter of the emulsion-casting solution. The final dried silver halide emulsion layer with such addition accordingly contains between 0.5 and 10 mgrof the compound per squarc meter.
By the addition of the phosphoric acid amide esters of the present invention to the emulsion or to the developer,
the ry-value in the development is shifted from about 6 to 8 to 15; Moreover, the period of development time during which the steepest gradation or screen dot sharpness is produced is raised from about 1 minute to 3 to 4 minutes. An additional advantage is that a developer containing formaldehyde is much less dependent'upon temperature when it has such an additive. Whereas a developer *without this additive reacts with a considerable development acceleration and thus a pronounced shortening of the development time when the temperature is raised by 1 to 2, good results are obtained with a developer temperature between 15 and 40 when phosphoric acid amide esters are added. Because of the longer processing period, the advantages described above lead to much more reliable Working. The compounds according to the invention can be'added to the developer composition in an amount of 0.01 to 10 grams per liter of the aqueous composition.
The phosphoric acid amide esters according to the invention are prepared by conventional esterification methods; the degree of condensation of the ester can be influenced as required by variations in the reaction time and in the reaction temperature. The higher the temperature, the higher is the. degree of condensation of the phosphoric acid amide esters, in particular the integer'Z" of the polyether ester formula can be influenced by varying the temperature. Thus, compounds were obtained in which Z had a value of about 100, 300, 800 or 1000. The degree' of condensation can further. be influenced, in particular the integer ,Z referred to hereinbefore, by varying the proportion of the starting compounds for theconden'sation. Compounds with a very high value of Z having rechain are obtained if the phosphoric acid amide reactant and the aliphatic polyether are reacted in a molar ,proportion of 1:1; Compounds containing only 1 phosphoric acid amide grouping are obtained if the phosphoric acid amide reactant and the polyether are reacted ina molar proportion of 1:2. Y
r In the following examples concerned with production, a number of condensation products are separately described:
' COMPOUND I 19 g. of N,N-diethylphosphoric acid amide-dichloride V are added in portions at temperatures between and with methylene chloride. After drying with potash, the
methylene chloride is completely evaporated. There are obtained 39 g. of a syrupy amber-coloured substance.
COMPOUND II 41.2 g. of nonaethylene glycol, 31.2 g. of pyridine and 19g. of N,N-diethyl phosphoric acid amidedichloride are reacted and worked up in the manner described above.
There are obtained 45 g. of a semi-solid, brown-coloured substance, which is diluted with water to a 10% solution and purified with activated carbon.
'COMPOUND III The preparation is similar to that of compound (I), by reaction of 28.2 g.'of hexaethylene glycol, 31.2 g. of pyridine and 22.4 g. of N-methyl-N-phenyl phosphoric acid amide dichloride. There are obtained 39 g. of a browncoloured, semi-solid substance, which is purified with activated carbon.
COMPOUND IV 41.4 g. of nonaethylene glycol, 31.2 'g. of pyridine and 22.4 g. of N-methyl-N-phenyl phosphoric acid amidedichloride are reacted in a manner analogous to Compound 'I. There are formed 50 g. of'a brown-coloured semi-solid substance, which is diluted with water and decolourised with activated carbon.
COMPOUND, v
1 mol of propylamidophosphoric acid diethyl ester is heated with approximately a 10% molar excess of octapeating phosphoric acid amide units in a wholly ether Grams Anhydrous sodium sulphite 30 Boric acid 7.5 Hydroquinone I 7 2 2.5
Potassium metabisulphite 2.5
P araformaldehyde 7.5
I Potassium bromide 1.5
ethylene glycol in the presence of'reesterification catalysts, such as sodium or sodium'alcoholate, for several hours at 100 to 120 C. The ethyl alcohol that is liberated is constantly distilled 01? in vacuo and the residue can be used I for the purpose of the present invention.
Example 1 A'gelatino-silver halide emulsion with 15 mol percent of AgBr and of AgCl is washed, ripened to the maximum sensitivity and, after adding 4-hydroxy-6-methyl- 1,3,3a,7-tetrazaindol or other stabilisers and a Wetting agent, cast onto a suitable film support; 7
Other film strips are prepared with the use of the same emulsions, 80 mg. of octaethylene glycol or 80 mg. of the Made up with water to 1 litre.
' In the sensitometric evaluation of the film strips, the following results are obtained:
Emulsion additive Gradation Fogging Octaethylene glyc0l 6 0. 04 Compoun 7 15 7 I 0.04 Compound IL- 15 0. 04' Compound III. 15 0. 04 Compound IV 15 0.04
Example 2 Film strips of the emulsion described in'Example 1 are exposed behind a grey stepped wedge and are developed in the developer referred to above for periods from 1 to 6 minutes (Experiment A). The same film specimens, after addition of mg. of the Compound I (Experiment B) and 100 mg. of the phosphorous acid glycol ester according to Example 1 of Belgian Patent 609,497 (Experiment C), are developed in the same developer. 1
Result A {Time Minutes. 1. 2 2. 5 3 4 5 6 'y-Value r 10 10 6 6 6 6 B {'Tirne, Minutes 1. 5 2 2. 5 3 4 5 6 v-value 8 10 10 10 10 10 8 C Time, Minutes. 1. 5 2 2. 5 3 4 5 6 7-value .1 10 10 10 8 6 6 6 Example 3 An emulsion as in Example 1 is given the usual additives (wetting agents, stabilisers and hardeners) and is divided into three portions and cast as follows onto a film support:
A: Without additive B: +80 mg. of the Compound 11 per mol of silver halide -C: +80 nag. of the analogous phosphoric acid glycol ester according to Example 3 of Belgian Patent No. 609,497. Several samples are cut from these webs and exposed in a sensitometer behind a grey stepped wedge and developed as follows in the aforementioned developer at 18 C.:
A {Time Minutes 1. 5 2 2. 5 3 4 5 6 'y-value 10 10 10 6 6 6 6 B {Time, Minutes. 1. 5 2 2. 5 3 4 5 6 v-value 8 10 10 10 10 10 8 C )Tirne, Minutes 1. 5 2 2. 5 3 4 5 6 L'y-value 10 10 10 6 6 6 6 We clarm:
1. In a process for developing an exposed photographic material containing at least 1 silver halide emulsion layer, the silver halide of which contains at least 50 mol percent of silver chloride, in a photographic aqueous developer composition containing formaldehyde, the improvement which consists in developing the exposed photographic material in contact with a reaction product of 1 to 2 mols of aliphatic polyether having terminal hydroxy groups, and 1 mol of a phosphoric acid amide derivative of the formula 111 which R is a radical of the group consisting of alkyl, phenyl, alkyl phenyl and phenyl alkyl; R is a substituent of the group consisting of hydrogen, alkyl, phenyl, alkyl phenyl and phenyl alkyl or R and R together are the methylene groups required to complete a heterocyclic radical of the group consisting of pyrrolidino and piperidino and X represents a substituent of the group consisting of chlorine, bromine and lower alkoxy.
2. A process as defined in claim 1, in which the reaction products has the following formula:
R1 R2 Z wherein R and R have the meaning defined in claim 1, m can be 0 and an integer from 3 to 10; n is an integer from 3 to 10 and Z is an integer from 1 to 1000.
3. A process as defined in claim 1, wherein the reaction product has the following formula 1|O-(CHz-CHz-O)n m N R1 R: Z
compound of the following formula 0 r l H HO-- CH2CII2O ]|?0 (CH2-CH2-O)11 H R1 R2 Z wherein R and R have the meaning defined in claim 1, m can be 0 and an integer from 3 to 10; n is an integer from 3 to 10 and Z is an integer from 1 to 1000.
5. An aqueous composition containing a silver halide photographic developer and from 0.01 to 10 grams per liter of a compound of the following formula:
wherein R and R have the meaning defined in claim 1, m can be 0 and an integer from 3 to 10; n is an integer from 3 to 10 and Z is an integer from 1 to 1000.
References Cited UNITED STATES PATENTS 3,156,718 11/1964 Lorenz et al. 260-461 3,157,685 11/1964 Szabo et a1. 26046l 3,158,483 11/1964 Lowe et al. 9666 3,162,534 12/1964 Powers et al. 96-66 NORMAN G. TORCHIN, Primary Examiner. C. E. DAVIS, Assistant Examiner.
Claims (1)
1. IN A PROCESS FOR DEVELOPING AN EXPOSED PHOTOGRAPHIC MATERIAL CONTAINING AT LEAST 1 SILVER HALIDE EMULSION LAYER, THE SILVER HALIDE OF WHICH CONTAINS AT LEAST 50 MOL PERCENT OF SILVER CHLORIDE, IN A PHOTOGRAPHIC AQUEOUS DEVELOPER COMPOSITION CONTAINING FORMALDEHYDE, THE IMPROVEMTN WHICH CONSISTS IN DEVELOPING THE EXPOSED PHOTOGRAPHIC MATERIAL IN CONTACT WITH A REACTION PRODUCT OF 1 TO 2 MOLS OF ALIPHATIC POLYETHER HAVING TERMINAL HYDROXY GROUPS, AND 1 MOL OF A PHOSPHORIC ACID AMIDE DERIVATIVE OF THE FORMULA
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DEA41899A DE1200682B (en) | 1962-12-17 | 1962-12-17 | Process for making photographic images |
Publications (1)
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US3346386A true US3346386A (en) | 1967-10-10 |
Family
ID=6932802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US329364A Expired - Lifetime US3346386A (en) | 1962-12-17 | 1963-12-10 | Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants |
Country Status (5)
Country | Link |
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US (1) | US3346386A (en) |
BE (1) | BE641382A (en) |
CH (1) | CH450914A (en) |
DE (1) | DE1200682B (en) |
GB (1) | GB1057948A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4471048A (en) * | 1981-07-10 | 1984-09-11 | Ciba Geigy Ag | Photographic material |
Citations (4)
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US3156718A (en) * | 1960-04-16 | 1964-11-10 | Bayer Ag | Process for preparing thiophosphoric, thiophosphonic, and thiophosphinic acid esters |
US3157685A (en) * | 1962-03-06 | 1964-11-17 | Stauffer Chemical Co | Partial esters of phosphoric acid and a method of preparing them |
US3158483A (en) * | 1957-03-08 | 1964-11-24 | Eastman Kodak Co | Photographic developers containing polyalkylene glycols |
US3162534A (en) * | 1962-05-14 | 1964-12-22 | Powers Chemco Inc | Photographic developer |
-
1962
- 1962-12-17 DE DEA41899A patent/DE1200682B/en active Pending
-
1963
- 1963-12-10 US US329364A patent/US3346386A/en not_active Expired - Lifetime
- 1963-12-13 CH CH1527963A patent/CH450914A/en unknown
- 1963-12-13 GB GB49357/63A patent/GB1057948A/en not_active Expired
- 1963-12-17 BE BE641382A patent/BE641382A/xx unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3158483A (en) * | 1957-03-08 | 1964-11-24 | Eastman Kodak Co | Photographic developers containing polyalkylene glycols |
US3156718A (en) * | 1960-04-16 | 1964-11-10 | Bayer Ag | Process for preparing thiophosphoric, thiophosphonic, and thiophosphinic acid esters |
US3157685A (en) * | 1962-03-06 | 1964-11-17 | Stauffer Chemical Co | Partial esters of phosphoric acid and a method of preparing them |
US3162534A (en) * | 1962-05-14 | 1964-12-22 | Powers Chemco Inc | Photographic developer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4471048A (en) * | 1981-07-10 | 1984-09-11 | Ciba Geigy Ag | Photographic material |
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Publication number | Publication date |
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DE1200682B (en) | 1965-09-09 |
CH450914A (en) | 1968-05-15 |
GB1057948A (en) | 1967-02-08 |
BE641382A (en) | 1964-06-17 |
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