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US3833378A - Developer composition for producing photographic materials for the graphic arts - Google Patents

Developer composition for producing photographic materials for the graphic arts Download PDF

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Publication number
US3833378A
US3833378A US00248275A US24827572A US3833378A US 3833378 A US3833378 A US 3833378A US 00248275 A US00248275 A US 00248275A US 24827572 A US24827572 A US 24827572A US 3833378 A US3833378 A US 3833378A
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Prior art keywords
developer composition
compound
composition
developer
ethylene oxide
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US00248275A
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K Hayashi
Y Iijima
T Kobayashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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

Definitions

  • ABSTRACT A developer composition for producing photographic materials for the graphic arts comprising a dihydroxy benzene developing agent and at least one polyethoxy amino compound represented by the following formula A mocmcm cinornonn 7)u ⁇ N( Hz)n -N H(OCH1C l)b (HiCHIO eH -'m CHzCHgOMH W V v A Formula (A) wherein n ranges from 2 to 10;
  • n m ranges from 0 to 6; and a +b +c+d+e X m ranges from 5 to 200 with a, b, c, d and 2 each representing an integer other than 0.
  • the present invention relates to a photographic developer composition for developing a high-contrast photographic element useful for the graphic arts.
  • Photographic line and halftone reproductions are carried out by imagewise'exposing a high-contrast or litho-type silver halide photographic element through a cross hatch screen or Contact screen and then developing it with a developer, whereby continuous tone images are converted into photographic line and halftone (dot) images.
  • the line and dot images be composed of only a maximum density portion and a background having a minimum density.
  • a high-contrast photographic element has the property of forming an intermediate density portion in addition to a maximum density portion and background, a portion of intermediate density which is termed fringe is always formed around the dot images. The formation of fringe is not desirable for graphic arts because it is deteriorates the dot qualities.
  • the fringe can be removed by using a so-called infectious developer composition which essentially contains a dihydroxybenzene type developing agent and a small amount of sulfite ion.
  • a dihydroxybenzene type developing agent for example, hydroquinone is converted into quinone during the development process and the resulting quinone reacts with sodium sulfite to produce sodium hydroquinonemonosulfonate.
  • sodium hydroquinonemonosulfanate is less reductive than hydroquinone due to its low electrode potential, and therefore is almost incapable of acting as a developing agent. Accordingly, the progress of development is not conducted rapidly, thus a fringe is formed.
  • the concentration of free sulfite ions is maintained at a low concentration, since sodium sulfite is added in a small amount and since it reacts with a compound having carbonyl groups, such as para-formaldehyde, incorporated in the infectious developer composition, in accordance with the following equation:
  • Infectious developer compositions of this kind therefore, have poor stability as compared to common black and white photographic developers, and the life of the infectious developer composition is short. Consequently, when infectious developer compositions are continuously used, images having a low contrast and a high fringe are obtained because the development is not carried out rapidly. Accordingly, it has been proposed to add an anti-oxidant other than sulfite to improve the stability. In this attempt, it is already known to add ascorbic acid into an infectious developer composition solution (Great Britain Pat. No. 928,390).
  • Ascorbic acid is, however, poor in stability and hence tends to be decomposed. Particularly, ascorbic acid tends to be decomposed when metal ions such as copper ions or iron ions are present in a developing solution. Further, it does not sufficiently stabilize the developer composition solution. Additionally, it has the drawbacks that the progress of development is slowed and that the dot quality is reduced when the ascorbic acid is added in a large amount.
  • An object of this invention is to provide a photographic developer composition for a high contrast photographic element useful for the graphic arts having an excellent stability unaccompanied by adverse influences on dot qualities.
  • Another object of the invention is to provide an infectious developer composition which is easily controlled before and during development.
  • Still another object of the invention is to provide an infectious developer composition in which the amount of replenishment during development is reduced.
  • a further object of the invention to provide a photographic development process for the graphic arts capable of forming line and dot images having good qualities by using an infectious developer composition stable for a long period of time.
  • m ranges from 0 to 6
  • a+b+c+d+(e m) ranges from 5 to 200 with a, b, c, d, and e each representing an integer other than (CI-IgCHqOhH Formula (B) wherein R represents an four carbon atoms with x y ranging from 3 to or R represents an -(CH CH O) I-I group with x y 2 Formula (A) techniques.
  • the compounds represented by the above-described formulaA used in the present invention can be produced by reacting commercially available compounds represented by the formula NHz
  • the compounds represented by the above-described formula B usedin the present invention are produced by reacting primary amines or monoethanol amines with ethyleneoxide in the desired molar amount using conventional techniques.
  • Ethylene oxide addition product of ethylenediamine (addition mol number, i.e., the amount of ethyleneoxy units added: 30)
  • the resulting photographic images obtained have little fringe and excellent halftone dots.
  • Sodium sulfite and ascorbic acid have the disadvantage that the quality of the halftone dots deteriorates if these materials are added in a large amount.
  • the compounds of the present invention do not deteriorate the quality of the halftone dots even though they are added in a large amount, as shown in examples hereinafter.
  • the compounds of the present invention are used in an infectious developer composition, a peculiar effect is obtained in that the halftone gradation becomes rich (soft) in addition to the preservability of the developer being improved without any deterioration of the quality of halftone dots. Accordingly, tone reproduction of an original is carried out more easily. Further, the development latitude (tolerance), that is the period during which optimum developing occurs, is prolonged and consequently it is easy to use.
  • the compounds of the present invention do not delay the proceeding of development. Rather they have a function of accelerating theproceeding of developmentwhenmis l or more anda+b+c+d+e X m is less than 10.
  • By use of compounds which accelerate the proceeding of development it is possible to carry out rapid treatment without elevating the temperature of the developer composition.
  • an infectious developer composition having a surprisingly long life and strong development activity by adding to an infectious developer composition of a low pH which has good preservability but poor development acitivity.
  • low pH means that the pH is lower than that of the common infectious developer composition, and more specifically it means a pH 9.8 or so.
  • An infectious developer composition in use, is basically composed of a dihydroxybenzene (developing agent), an alkali, a small amount of sulfite and, if necessary, a sulfite ion buffer.
  • the infectious developer composition of the invention further contains the aforesaid polyethoxy amino compound.
  • Dihydroxybenzenes are known in the art and can be easily selected by one skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc.
  • hydroquinone is preferably used. These developing agents are used singly or in combination.
  • a suitable'amount of the developing agent to be added ranges from about 5 to 50 g., preferably about 10 to 30 g., per 1 liter of the developer composition.
  • a sulfite ion buffer can be used in such an amount that concentration of sulfite is maintained at a low level in the developer composition.
  • buffers are an aldehyde-alkali metal hydrogen sulfite addition product such as formalin-sodium hydrogen sulfite, a
  • the sulfite ion buffer is not limited to the above examples and each ingredient of the addition product or condensation product may be added to the developer.
  • the amount of the sulfite ion buffer which is added can range from about 13 to 130 g., preferably 30 to 60 g. per one liter of the developer composition.
  • An alkali is added to adjust the developer composition to an alkaline condition preferably to a pH higher than 8, more preferably to apH of 9 to 11. Accordingly, the addition amount and kind of additive can be freely selected and is not limited to the above examples.
  • the developersolution can contain further a pH buffer agent, such as an alkanolamine, a water-soluble acid (e.g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate). Further, it may contain an alkali metal halide as a development controlling agent.
  • a pH buffer agent such as an alkanolamine, a water-soluble acid (e.g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate).
  • a salt e.g., sodium carbonate
  • an organic anti-fogging agent e.g., .benzotriazole, lphenyl-S-mercapto-tetrazole
  • a polyalkylene oxide e.g., 1,3-bis(trimethoxy)-2-aminoethyl-N-phenyl-N-phenyl-S-mercapto-tetrazole
  • an organic solvent e.g., triethylene glycol, dimethylformamide, methanol, cellosolve
  • a characteristic of the infectious developer solution is that the concentration of free sulfite is low.
  • a sulfite ion buffer material such as formaldehyde-sodium bisulfite adduct is generally employed.
  • the concentration of free sulfite ions is controlled by the addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per 1 liter of the developer solution as well as a sulfite ion buffer agent.
  • an alkali metal sulfite such as sodium sulfite
  • 'Sulfite is generally added in an amount of not more than 3 g per liter of the developer solution, and thereby the stability of the developer solutionis slightly improved, although the dot quality is more or less reduced. However, as described above, this degree of the stability is generally not satisfactory.
  • the compounds of the present invention improve the inherently poor stability of an infectious developer solution which does not contain an alkali sulfite other than a sulfite ion buffer agent such as a formaldehydesodium bisulfite adduct to a certain extent, they remarkably improve the stability of an infectious developer solution which contains both an alkali sulfite in an amount of not more than 5 g per 1 liter of the developer solution (0.005 0.05 mole of free sulfite) and a sulfite ion buffer agent.
  • a sulfite ion buffer agent such as a formaldehydesodium bisulfite adduct
  • the compounds of the present invention exert an effect even in a developer solution which does not contain a free sulfite (e.g., a developer solution which does not contain a sulfite other than formaldehyde-bisulfite adduct), but this effect is very small. Accordingly, from a practical standpoint the present invention can be employed best in a developer solution containing a small amount of free sulfite.
  • a single compound of this invention or a combi nation of two or more compounds of this invention can be used.
  • the amount of the compounds of the present invention added to a developer solution varies according to the composition of the developing solution and the kind of the compounds used, but the amount employed generally is in the range of from 0.1 g to 100 g per 1 liter of the developing solution, more preferably from 0.1 g to 60 g per 1 liter of the developer solution.
  • the developing compounds When the developing compounds are processed prior to use so that they may be readily used as developer solutions on mixing with water or dissolving in water, that is, when they are in the form of liquid or powdered developer compositions, it is effective to incorporate the compounds of the present invention into the developer preparations beforehand.
  • liquid preparations When liquid preparations are used, it is particularly effective to add the compounds of the present invention since they improve remarkably the stability of the liquid preparations.
  • Liquid preparations generally are not known to have a good stability, and therefore it is difficult to obtain a stable developer composition, since the liquid preparations can not con-- tain a large amount of salts (e. g., carbonylbisulfite) due to the characteristics of liquid preparations. Therefore, it is particularly desirable to use the hydrazine compounds of the present invention in liquid preparations.
  • a general liquid preparation comprises two liquid compositions, that is, a liquid component containing the developing agent and a liquid component containing a alkali.
  • the compounds of the present invention may be incorporated into any such components, but, it
  • solvents for the liquid developing agent there may be used solvents such as water, benzyl alcohol, ethylene glycol,,diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents.
  • solvents such as water, benzyl alcohol, ethylene glycol,,diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents.
  • Light-sensitive materials for printing used in the present invention, include common silver halide emulsions (e.g., silver chloride emulsions, silver chlorobromide emulsions, silver chloroiodobromide emulsions). Particularly, silver chlorobromide emulsions and silver 7 chloroiodobromide emulsions, containing not less than about 50 mole percent of silver chloride, are suitable for the present invention.
  • silver chlorobromide emulsions and silver 7 chloroiodobromide emulsions containing not less than about 50 mole percent of silver chloride, are suitable for the present invention.
  • hydrophilic colloidal substances such as gelatin or gelatin derivatives (e.g., collodion), hydroxyethylcellulose, carboxymethylcellulose; water-soluble starches (e.g., dextrin, alkali starch); or hydrophilic polymers (e.g., polyvinyl alcohols, polyvinyl pyrrolidines, polyacrylamides, polystyrenesulfonic acids) can be used.
  • These light-sensitive materials may contain additionally hydrophobic polymers such as polyacrylates, and gelatinplasticizers such as glycerin or trimethanolpropane.
  • the emulsions used in these light-sensitive materials may be sensitized using various techniques either when the materials are manufactured or when the materials are applied. For example, they may be chemically sensitized by methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complexes of monovalent gold and thi- ,7 I ocyanic acid,or mixtures of these. Further, the emulsions may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium. In addition, the emulsions may bepanchromatically or orthochromatically sensitized with color-sensitizers such as cyanine dyes or merocyanine dyes.
  • the emulsions may contain dot quality-improving agents such as polyalkyleneoxides and amine compounds (US. Pat. No. 3,288,612, German Specification OLS 1,932,882, US. Pat. No. 3,345,175) and sodium benzenethiosulfate, benzenetriazole and 1,3,3a, 7-tetrazaindene derivatives (US. Pat. No. 3,375,114 or US. Pat. No. 3,333,959).
  • the emulsions may be hardened with formaldehyde, resorcylaldehyde, dimethylol urea, 2, 4dichloro-6- hydroxy-l,3,5-triazine (US. Pat. No.
  • emulsions may further contain agents which improve the progress of development such as 3-pyrazolidone derivatives or pyrazolone deriv- Developer Composition A Sodium Carbonate (monohydrate) Formaldehyde-Sodium Hydrogen Sulfite Addition Product Potassium Bromide Hydroquinone Sodium Sulfite Water to make h U1 -NOONUI 510000050 2 0n :0
  • Developer Composition C Developer Composition C was produced by adding 40 g/l. of Compound 2 of the present invention to Deatives. Further,'the emulsion may contain development-accelerating'agents such as quaternary ammonium salts or cationic surface-active agents. .
  • the supports used in the present invention are not limited, and glass, cellulose acetate, polystyrene, polycarbonate, polyethylene terephthalate and the like may be used.
  • the Halftone Gradation shows number of stages of from 10 percent halftone dot to 90 percent halftone dot.
  • the aerated liquid means a developer composition which was subjected to deterioration by contacting 500 ml of the developer composition in a 20 cm X 25 cm developing vat with air for 5 hours.
  • the compounds of the present invention improve the stability of the developer compositions without having a large influence upon photographic properties and have the function of softening the halftone gradation.
  • Developer Compositions G. H and I were produced by adding the following compounds respectively to Developer Composition.
  • F the pH of the resulting developer compositions were the same as in Developer Com- Sodium Sulfite 10 EXAMPLE 3.
  • Developer Composition L was prepared by adding 0.5 g/l. of Compound 7 to the above-described composition and adjusting the pH to 9.80.
  • Developer Composition M was prepared by adding 0.1 g/l. of Compound 8 and 20 g/l. of Compound 6 to the above-described composition and adjusting the pH The results obtained are shown in Table 3.
  • the aerated liquid is a developer composition which was subjected to deterioration by contacting 500 ml of the developer composition in a cm X cm developing'vat with air for 24 hours.
  • a film having the same properties can be obtained by developing using a developer composition having a pH of 10.30 which is prepared by adding 0.15g/l. of Compound 8 to Developer Composition F using an automatic developing apparatus for plate making for 35 seconds (temperature of development 27C) as was obtained by developing with Developer Composition F for 90 seconds.
  • An infectious photolithographic developer composition for producing photographic materials for the graphic arts comprising a hydroquinone or hydroquinone derivative developing agent, 0.005 to 0.05 mol free sulfite per. liter, and at leastone polyethoxyamino compound represented by the following formula A:
  • n ranges from 2 to 10;
  • n 0 to 6; and a b c d e X m ranges from 5 to 200 with a,
  • composition of claim 1 wherein said composition additionally contains an aldehydealkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
  • said developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, or 2,5-dimethylhydroquinone.
  • diethylenetriamine having an addition mol number of said compound is an ethylene oxide addition product of tetraethylenepentamine having an addition mol number of 10.

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

Abstract

A developer composition for producing photographic materials for the graphic arts comprising a dihydroxy benzene developing agent and at least one polyethoxy amino compound represented by the following formula A

wherein n ranges from 2 to 10; M RANGES FROM 0 TO 6; AND A + B + C + D + E X M RANGES FROM 5 TO 200 WITH A, B, C, D AND E EACH REPRESENTING AN INTEGER OTHER THAN 0. OR THE FORMULA B

wherein R represents an alkyl group of less than four carbon atoms, where C4 x X y ranges from 3 to 100 or R represents a (CH2CH2O)zH group, where x + y + z ranges from 5 to 100, in which x, y and z each represent an integer other than 0 is disclosed.

Description

[ Sept. 3, 1974 DEVELOPER COMPOSITION FOR PRODUCING PHOTOGRAPHIC MATERIALS FOR THE GRAPHIC ARTS [75] Inventors: Katsumi Hayashi; Yoo Iijima; Teruo Kobayashi, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,
Kanagawa, Japan [22] Filed: 7 Apr. 27, 1972 [21] Appl. No.1 248,275
[30] Foreign Application Priority Data a Apr. 27, 1971 Japan 46-27816 [52] US. Cl. 96/66.3, 96/66 R [51] Int. Cl G03c 5/30 [58] Field of Search...; 96/66, 66.3, 107
[5 6] References Cited UNITED STATES PATENTS 3,062,647 11/1962 Herz 96/66.3 3,128,183 4/1964 Jones 3,426,029 2/1969 Beavers... 3,622,330 11/1971 Valiaveedan 96/66.3
FOREIGN PATENTS OR APPLICATIONS 45-6630 1970 Japan 96/66.3 748,745 1956 Great Britain 96/107 Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [5 7 ABSTRACT A developer composition for producing photographic materials for the graphic arts comprising a dihydroxy benzene developing agent and at least one polyethoxy amino compound represented by the following formula A mocmcm cinornonn 7)u{ N( Hz)n -N H(OCH1C l)b (HiCHIO eH -'m CHzCHgOMH W V v A Formula (A) wherein n ranges from 2 to 10;
m ranges from 0 to 6; and a +b +c+d+e X m ranges from 5 to 200 with a, b, c, d and 2 each representing an integer other than 0.
or the formula B 20 Claims, No Drawings DEVELOPER COMPOSITION FOR PRODUCING PHOTOGRAPHIC MATERIALS FOR THE GRAPHIC ARTS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic developer composition for developing a high-contrast photographic element useful for the graphic arts.
2. Description of the Prior Art Photographic line and halftone reproductions are carried out by imagewise'exposing a high-contrast or litho-type silver halide photographic element through a cross hatch screen or Contact screen and then developing it with a developer, whereby continuous tone images are converted into photographic line and halftone (dot) images.
It is most desirable that the line and dot images be composed of only a maximum density portion and a background having a minimum density. However, since a high-contrast photographic element has the property of forming an intermediate density portion in addition to a maximum density portion and background, a portion of intermediate density which is termed fringe is always formed around the dot images. The formation of fringe is not desirable for graphic arts because it is deteriorates the dot qualities.
As is well known in the art, the fringe can be removed by using a so-called infectious developer composition which essentially contains a dihydroxybenzene type developing agent and a small amount of sulfite ion. In a conventional developer composition, a dihydroxybenzene type developing agent, for example, hydroquinone is converted into quinone during the development process and the resulting quinone reacts with sodium sulfite to produce sodium hydroquinonemonosulfonate. However, sodium hydroquinonemonosulfanate is less reductive than hydroquinone due to its low electrode potential, and therefore is almost incapable of acting as a developing agent. Accordingly, the progress of development is not conducted rapidly, thus a fringe is formed. In contrast to this, where an infectious developer composition is used, the concentration of free sulfite ions is maintained at a low concentration, since sodium sulfite is added in a small amount and since it reacts with a compound having carbonyl groups, such as para-formaldehyde, incorporated in the infectious developer composition, in accordance with the following equation:
cazo Na SO H20 2 CH ONaI-ISO NaOH For this reason, in the development process it becomes difficult for the quinone to react with sulfurous acid to produce hydroquinonemonosulfonic acid, and
thereby the concentration of quinone is increased. The thus produced quinone and the original hydroquinone cause a dispropor'tionation reaction and produce semiquinone. The semiquinone reduces silver halide and itself is converted to quinone due to its high developing activity. The description by Yule in J. Frank 1nst., 239, page 221 (1945) is that a rapid development is brought by the successive repetition of this procedure, thus giving a development with a high gamma.
While a sulfite is well known as one of the preservatives for a photographic developer composition, it is necessary to decrease the concentration of sulfite in 2- order to obtain more effective line and dot reproductions.
Infectious developer compositions of this kind, therefore, have poor stability as compared to common black and white photographic developers, and the life of the infectious developer composition is short. Consequently, when infectious developer compositions are continuously used, images having a low contrast and a high fringe are obtained because the development is not carried out rapidly. Accordingly, it has been proposed to add an anti-oxidant other than sulfite to improve the stability. In this attempt, it is already known to add ascorbic acid into an infectious developer composition solution (Great Britain Pat. No. 928,390).
Ascorbic acid is, however, poor in stability and hence tends to be decomposed. Particularly, ascorbic acid tends to be decomposed when metal ions such as copper ions or iron ions are present in a developing solution. Further, it does not sufficiently stabilize the developer composition solution. Additionally, it has the drawbacks that the progress of development is slowed and that the dot quality is reduced when the ascorbic acid is added in a large amount.
An object of this invention is to provide a photographic developer composition for a high contrast photographic element useful for the graphic arts having an excellent stability unaccompanied by adverse influences on dot qualities.
Another object of the invention is to provide an infectious developer composition which is easily controlled before and during development.
Still another object of the invention is to provide an infectious developer composition in which the amount of replenishment during development is reduced.
A further object of the invention to provide a photographic development process for the graphic arts capable of forming line and dot images having good qualities by using an infectious developer composition stable for a long period of time.
SUMMARY OF THE INVENTION H OCHIOHZ (CHzCHzO) CH wherein n range from 2 to 10,
. m ranges from 0 to 6 a+b+c+d+(e m) ranges from 5 to 200 with a, b, c, d, and e each representing an integer other than (CI-IgCHqOhH Formula (B) wherein R represents an four carbon atoms with x y ranging from 3 to or R represents an -(CH CH O) I-I group with x y 2 Formula (A) techniques.
ranging from to 100, and x, y and 2 represent each an integer other than 0.
DETAILED DESCRIPTION OF THE INVENTION The compounds represented by the above-described formulaA used in the present invention can be produced by reacting commercially available compounds represented by the formula NHz The compounds represented by the above-described formula B usedin the present invention are produced by reacting primary amines or monoethanol amines with ethyleneoxide in the desired molar amount using conventional techniques.
In the following, representative compounds within the above-described formulae which can be used in the present invention are shown.
Compound 1: v
Ethylene oxide addition product of ethylenediamine (addition mol number, i.e., the amount of ethyleneoxy units added: 30)
Compound 2:
' Ethylene oxide addition product of hexamethylenediamine (addition mol number: 5)
Compound 3: V v
Ethylene oxide addition product of trimethylenediamine (addition mol number: 30) 4 Compound 4:
Ethylene oxide addition product of diethylenetriamine (addition mol number: 50)
Compound 5:
Ethylene oxide addition product of tetraethylenepentamine (addition mol number: 50) Compound 6:
Ethylene oxide addition product of triethylenetetramine (addition mole number: 100 Compound 7:
Ethylene oxide addition product of diethylenetriamine (addition mole number: Compound 8:
Ethylene oxide addition product of tetraethylenepentamine (addition mol number: 10) V Compound 9:
N,N-Di-polyoxyethylene ethylamine (addition mol number: 5)
Compound 10: I
N,N,N-Tr'i-polyoxyethyleneamine (addition mol number: 50)
Compound l li i N,N-D i-polyoxyethylene butylamine (addition mol number: 80) l V Use of the compounds of the present invention to photographic developer compositions is unknown, and particularly it is entirely unknown to improve the stability characteristics of developercompositions by adding to a developer of photographic materials for the graphic arts. As the result of examination of many com- X m) using conventional pounds, the present inventors have found the compounds represented by the above-described formulae improve the preservation characteristics of the developer. Why the preservation characteristics are improved by adding these compounds to the developer composition of photographic negatives for printing is not yet completely understood. But the preservability of the developer composition is improved in comparison with the known use of sodium sulfite or ascorbic acid etc. and the resulting photographic images obtained have little fringe and excellent halftone dots. Sodium sulfite and ascorbic acid have the disadvantage that the quality of the halftone dots deteriorates if these materials are added in a large amount. However, the compounds of the present invention do not deteriorate the quality of the halftone dots even though they are added in a large amount, as shown in examples hereinafter.
When the compounds of the present invention are used in an infectious developer composition, a peculiar effect is obtained in that the halftone gradation becomes rich (soft) in addition to the preservability of the developer being improved without any deterioration of the quality of halftone dots. Accordingly, tone reproduction of an original is carried out more easily. Further, the development latitude (tolerance), that is the period during which optimum developing occurs, is prolonged and consequently it is easy to use.
The compounds of the present invention do not delay the proceeding of development. Rather they have a function of accelerating theproceeding of developmentwhenmis l or more anda+b+c+d+e X m is less than 10. By use of compounds which accelerate the proceeding of development, it is possible to carry out rapid treatment without elevating the temperature of the developer composition. Further, it is possible to obtain an infectious developer composition having a surprisingly long life and strong development activity by adding to an infectious developer composition of a low pH which has good preservability but poor development acitivity. In the present specification, low pH means that the pH is lower than that of the common infectious developer composition, and more specifically it means a pH 9.8 or so.
An infectious developer composition, in use, is basically composed of a dihydroxybenzene (developing agent), an alkali, a small amount of sulfite and, if necessary, a sulfite ion buffer. The infectious developer composition of the invention further contains the aforesaid polyethoxy amino compound.
Dihydroxybenzenes are known in the art and can be easily selected by one skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc. As developing agents, hydroquinone is preferably used. These developing agents are used singly or in combination. A suitable'amount of the developing agent to be added ranges from about 5 to 50 g., preferably about 10 to 30 g., per 1 liter of the developer composition.
A sulfite ion buffer can be used in such an amount that concentration of sulfite is maintained at a low level in the developer composition. Examples of such buffers are an aldehyde-alkali metal hydrogen sulfite addition product such as formalin-sodium hydrogen sulfite, a
ketone-alkali metal hydrogen sulfite addition product such as acetone-sodium hydrogen sulfite addition product, and a carbonylbisulfiteamine condensation product such as sodium bis-(2-hydroxyethyl)- aminomethane sulfonate. The sulfite ion buffer is not limited to the above examples and each ingredient of the addition product or condensation product may be added to the developer. The amount of the sulfite ion buffer which is added can range from about 13 to 130 g., preferably 30 to 60 g. per one liter of the developer composition.
An alkali is added to adjust the developer composition to an alkaline condition preferably to a pH higher than 8, more preferably to apH of 9 to 11. Accordingly, the addition amount and kind of additive can be freely selected and is not limited to the above examples. I
The developersolution can contain further a pH buffer agent, such as an alkanolamine, a water-soluble acid (e.g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide) or a salt (e.g., sodium carbonate). Further, it may contain an alkali metal halide as a development controlling agent. Also, it may contain in some cases an organic anti-fogging agent (e.g., .benzotriazole, lphenyl-S-mercapto-tetrazole), a polyalkylene oxide, an amine, and an organic solvent (e.g., triethylene glycol, dimethylformamide, methanol, cellosolve) in an amount of not more than 300 ml per 1 liter of the developer solution. I
As described above, a characteristic of the infectious developer solution is that the concentration of free sulfite is low. For this purpose a sulfite ion buffer material such as formaldehyde-sodium bisulfite adduct is generally employed. v
In general, the concentration of free sulfite ions is controlled by the addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per 1 liter of the developer solution as well as a sulfite ion buffer agent. 'Sulfite is generally added in an amount of not more than 3 g per liter of the developer solution, and thereby the stability of the developer solutionis slightly improved, although the dot quality is more or less reduced. However, as described above, this degree of the stability is generally not satisfactory. Although the compounds of the present invention improve the inherently poor stability of an infectious developer solution which does not contain an alkali sulfite other than a sulfite ion buffer agent such as a formaldehydesodium bisulfite adduct to a certain extent, they remarkably improve the stability of an infectious developer solution which contains both an alkali sulfite in an amount of not more than 5 g per 1 liter of the developer solution (0.005 0.05 mole of free sulfite) and a sulfite ion buffer agent. That is to say, the compounds of the present invention exert an effect even in a developer solution which does not contain a free sulfite (e.g., a developer solution which does not contain a sulfite other than formaldehyde-bisulfite adduct), but this effect is very small. Accordingly, from a practical standpoint the present invention can be employed best in a developer solution containing a small amount of free sulfite. A single compound of this invention or a combi nation of two or more compounds of this invention can be used. The amount of the compounds of the present invention added to a developer solution varies according to the composition of the developing solution and the kind of the compounds used, but the amount employed generally is in the range of from 0.1 g to 100 g per 1 liter of the developing solution, more preferably from 0.1 g to 60 g per 1 liter of the developer solution.
When the developing compounds are processed prior to use so that they may be readily used as developer solutions on mixing with water or dissolving in water, that is, when they are in the form of liquid or powdered developer compositions, it is effective to incorporate the compounds of the present invention into the developer preparations beforehand. When liquid preparations are used, it is particularly effective to add the compounds of the present invention since they improve remarkably the stability of the liquid preparations. Liquid preparations generally are not known to have a good stability, and therefore it is difficult to obtain a stable developer composition, since the liquid preparations can not con-- tain a large amount of salts (e. g., carbonylbisulfite) due to the characteristics of liquid preparations. Therefore, it is particularly desirable to use the hydrazine compounds of the present invention in liquid preparations.
A general liquid preparation comprises two liquid compositions, that is, a liquid component containing the developing agent and a liquid component containing a alkali. The compounds of the present invention may be incorporated into any such components, but, it
is particularly effective to add them to the component containing the developing agent. With this treatment, a liquid developing agent having an excellent stability and an infectious developer solution prepared by dilution of said liquid developing agent having a markedly excellent stability, can be obtained.
As solvents for the liquid developing agent, there may be used solvents such as water, benzyl alcohol, ethylene glycol,,diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents. Alternatively, it is possible to improve the stability of the developer solution by adding the compounds of the present invention in the course of development or after development of the photographic materials for printing.
Light-sensitive materials for printing, used in the present invention, include common silver halide emulsions (e.g., silver chloride emulsions, silver chlorobromide emulsions, silver chloroiodobromide emulsions). Particularly, silver chlorobromide emulsions and silver 7 chloroiodobromide emulsions, containing not less than about 50 mole percent of silver chloride, are suitable for the present invention. As silver halide-dispersing agents containing these light-sensitive materials, hydrophilic colloidal substances, such as gelatin or gelatin derivatives (e.g., collodion), hydroxyethylcellulose, carboxymethylcellulose; water-soluble starches (e.g., dextrin, alkali starch); or hydrophilic polymers (e.g., polyvinyl alcohols, polyvinyl pyrrolidines, polyacrylamides, polystyrenesulfonic acids) can be used. These light-sensitive materials may contain additionally hydrophobic polymers such as polyacrylates, and gelatinplasticizers such as glycerin or trimethanolpropane.
The emulsions used in these light-sensitive materials may be sensitized using various techniques either when the materials are manufactured or when the materials are applied. For example, they may be chemically sensitized by methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complexes of monovalent gold and thi- ,7 I ocyanic acid,or mixtures of these. Further, the emulsions may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium. In addition, the emulsions may bepanchromatically or orthochromatically sensitized with color-sensitizers such as cyanine dyes or merocyanine dyes. Yet further, the emulsions may contain dot quality-improving agents such as polyalkyleneoxides and amine compounds (US. Pat. No. 3,288,612, German Specification OLS 1,932,882, US. Pat. No. 3,345,175) and sodium benzenethiosulfate, benzenetriazole and 1,3,3a, 7-tetrazaindene derivatives (US. Pat. No. 3,375,114 or US. Pat. No. 3,333,959). The emulsions may be hardened with formaldehyde, resorcylaldehyde, dimethylol urea, 2, 4dichloro-6- hydroxy-l,3,5-triazine (US. Pat. No. 3,325,287) or mucochloric acid, or they may contain surface-active agents such as saponin in order to facilitate the application of the emulsions. The emulsions may further contain agents which improve the progress of development such as 3-pyrazolidone derivatives or pyrazolone deriv- Developer Composition A Sodium Carbonate (monohydrate) Formaldehyde-Sodium Hydrogen Sulfite Addition Product Potassium Bromide Hydroquinone Sodium Sulfite Water to make h U1 -NOONUI 510000050 2 0n :0
Developer Composition C Developer Composition C was produced by adding 40 g/l. of Compound 2 of the present invention to Deatives. Further,'the emulsion may contain development-accelerating'agents such as quaternary ammonium salts or cationic surface-active agents. .The supports used in the present invention are not limited, and glass, cellulose acetate, polystyrene, polycarbonate, polyethylene terephthalate and the like may be used.
The present invention will now be illustrated in greater detail by the following examples.
veloper Composition A (the pH was the same as in Developer Composition A). Developer Composition D Developer Composition D was produced by adding 5 g/l. l. of sodium sulfite to Developer A (the pH was the same as in Developer Composition A). Developer Composition E Developer Composition E was produced by adding 1 g/l. of ascorbic acid to Developer Composition A (the pH was the same as in Developer Composition A). The results obtained using the above are shown in Table 1.
Table 1 Developer Additive Development Halftone Halftone Sensitivity Composi- Time Dot Grada- Fresh Aerated tion Quality tion Liquid Liquid (second) i (5 hours) B Compound 1 90 a l7 lOO 80 C Compound 2 90 a I6 100 85 D Sodium Sulfate 120 c 14 100 60 E Ascorbic Acid I a 15 I00 55 EXAMPLE 1 A lithofilm was produced by carrying out gold sensitization and sulfur sensitizationof a silver halide emulsion comprising 75 mol percent silver chloride, 0.2 mol percent silver iodide and the balance of silver bromide, carrying out optical sensitization using 3- carboxymethyl-5-[2-(3-ethylthiazolinylidene)ethylidene]rhodamine, adding polyoxyethylene nonylphenyl ether containing ethylene oxide groups and a development accelerating agent The Development Time is that time for reaching the sensitivity obtained on development using Developer Composition A for seconds (this sensitivity is set for The Halftone Dot Quality was evaluated and the results are shown in Table 1 using an a, b, and c ranking system, in which a means good, b means somewhat good and 0 means bad. The Halftone Gradation shows number of stages of from 10 percent halftone dot to 90 percent halftone dot. The aerated liquid means a developer composition which was subjected to deterioration by contacting 500 ml of the developer composition in a 20 cm X 25 cm developing vat with air for 5 hours.
As can be seen from the results contained in the above table, the compounds of the present invention improve the stability of the developer compositions without having a large influence upon photographic properties and have the function of softening the halftone gradation.
' EXAMPLE 2 (3-ethylthiazolinilidene)ethylidene]rhodonine, then, thereto were added a polyoxyethylene nonylphenylether containing 50 ethyleneoxide groups, the development-accelerating agent Developer Composition F Solution 1:
Water 60 ml Triethylenc Glycol 30 ml Formaldehyde-Sodium Hydrogen Sulfite Addition Product 45 g Sodium Sulfite l g Hydroquinone 16 g Water to make 125 ml Solution ll:
Water 100 ml Sodium Carbonate (monohydrate) 30 g Sodium Hydroxide Y 5 g Boric Acid 3 g Sodium Bromide 2 g Water to make 125 ml On use, Solution I is added to 750 ml of water and So-' lution II is then added thereto to make 1 liter.
Developer Compositions G. H and I were produced by adding the following compounds respectively to Developer Composition. F (the pH of the resulting developer compositions were the same as in Developer Com- Sodium Sulfite 10 EXAMPLE 3.
The same effect is obtained with using the following solution as the supplemental solution for developer F in Example 2.
S pplement Solution Triethylene Glycol ml Formaldehyde-Sodium Sulfite Addition Product g Sodium Sulfite l g Soldium Carbonate (monohydrate) 25 g 15 Hydroquinone 18 g Boric Acid 4 g Compound 5 g Triethanol Amine 10 ml Water to make 1 liter EXAMPLE 4. 7 With using a litho film as described in Example 1, an
2 exposing wedge for sensitometry was photographed th-' rough a 150 line magenta contact screen. Then, the film was developed using four kinds of developers having the following compositions at 27C.
Developer Composition Sodium Carbonate (monohydrate) 5 Formaldehyde-Sodium Hydrogen Y Sulfite Addition Product 4 Potassium Bromide Hydroquinone l NOONM o UQOQOQUQ on Sodium Hydroxide or Acetic Acid Amount necessary to control pH.
Waterto make 1 liter Developer Composition J was prepared using the position F). above-described composition and adjusting the pH to The results obtained are shown in Table 2. 10.30. v
' Table 2 Developer Additive Amount Halftone Halftone Sensitivity Composi Dot Grada- Fresh Aerated tion Quality tion Liquid Liquid (g/U (two days) F I a lo 100 30 G Compound 3 5 a 18 100 97 H Compound 4 20 a 17 100 100 1 Compound l0 13 a 18 100 95 Developer Composition K was prepared using the above-described composition and adjusting the pH to 9.80.
Developer Composition L was prepared by adding 0.5 g/l. of Compound 7 to the above-described composition and adjusting the pH to 9.80.
Developer Composition M was prepared by adding 0.1 g/l. of Compound 8 and 20 g/l. of Compound 6 to the above-described composition and adjusting the pH The results obtained are shown in Table 3.
Table 3 Developer Additive pH 7 Development Halftone Sensitivity Composi- Time Dot Fresh Aerated tion Quality Liquid Liquid (second) (2 1 hours) I 10.30 90 a l 10 K 9.80 240 a I00 50 L Compound 7- 9.80 90 a 100 98 M Compound 8 1 9.80 90 a I00 100 The aerated liquid is a developer composition which was subjected to deterioration by contacting 500 ml of the developer composition in a cm X cm developing'vat with air for 24 hours. g
In developer compositions having a low pH, although the preservability is excellent, the development time is markedly long. However, when the compounds of the present invention having a development accelerating property are used together, the stability is markedly improved without delaying the development time.
EXAMPLE 5.
A film having the same properties can be obtained by developing using a developer composition having a pH of 10.30 which is prepared by adding 0.15g/l. of Compound 8 to Developer Composition F using an automatic developing apparatus for plate making for 35 seconds (temperature of development 27C) as was obtained by developing with Developer Composition F for 90 seconds.
What is claimed is:
1. An infectious photolithographic developer composition for producing photographic materials for the graphic arts comprising a hydroquinone or hydroquinone derivative developing agent, 0.005 to 0.05 mol free sulfite per. liter, and at leastone polyethoxyamino compound represented by the following formula A:
wherein n ranges from 2 to 10;
m ranges from 0 to 6; and a b c d e X m ranges from 5 to 200 with a,
b, c, d and e each representing an interger other than 0.
2. The developer composition of claim 1, wherein said composition additionally contains an aldehydealkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
3. The developer composition of claim 2, wherein said composition contains formaldehyde-sodium bisulfite adduct.
4. The developer composition of claiml, wherein said developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone,'
toluhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, or 2,5-dimethylhydroquinone.
5. The developer composition of claim 4, wherein said developing agent is hydroquinone.
6. The developer composition of claim 1, wherein said polyethoxy amino compound is present at a level ranging'from 0.1 g to 100 g per liter of the developer composition and wherein said developing agent is present at a level ranging from 5 to 50 g per liter of developer composition.
10. The method of claim 7, wherein said developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, or 2,5-dimethylhydroquinone.
11. The method of claim 10, wherein said developing agent is hydroquinone.
12. The method of claim 7, wherein said polyethoxy amino compound is present at a level ranging from 0.1 g to g per liter of developer composition and wherein said developing agent is present at a level ranging from 5 to 50 g per liter of developer composition.
13. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of ethylenediamine having an addition mol number of 30.
14. The devloper composition of claim 1, wherein said compound is an ethylene oxide addition product of hexamethylenediamine having an addition mol number of 5.
15. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of trimethylenediamine having an addition mol number of 30. I
16. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of diethylenetriamine having an addition mol number of 50.
diethylenetriamine having an addition mol number of said compound is an ethylene oxide addition product of tetraethylenepentamine having an addition mol number of 10.
20. The developer composition of claim 1, wherein I

Claims (19)

  1. 2. The developer composition of claim 1, wherein said composition additionally contains an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
  2. 3. The developer composition of claim 2, wherein said composition contains formaldehyde-sodium bisulfite adduct.
  3. 4. The developer composition of claim 1, wherein said developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
  4. 5. The developer composition of claim 4, wherein said developing agent is hydroquinone.
  5. 6. The developer composition of claim 1, wherein said polyethoxy amino compound is present at a level ranging from 0.1 g to 100 g per liter of the developer composition and wherein said developing agent is present at a level ranging from 5 to 50 g per liter of developer composition.
  6. 7. A method for producing a photographic line of half-tone reproduction in the graphic arts comprising exposing a high contrast photographic element and developing said exposed element in the developer composition of claim 1.
  7. 8. The method of claim 7, wherein said composition additionally contains a aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
  8. 9. The method of claim 8, wherein said composition contains formaldehyde-sodium busulfite adduct.
  9. 10. The method of claim 7, wherein said developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, or 2,5-dimethylhydroquinone.
  10. 11. The method of claim 10, wherein said developing agent is hydroquinone.
  11. 12. The method of claim 7, wherein said polyethoxy amino compound is present at a level ranging from 0.1 g to 100 g per liter of developer composition and wherein said developing agent is present at a level ranging from 5 to 50 g per liter of developer composition.
  12. 13. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of ethylenediamine having an addition mol number of 30.
  13. 14. The devloper composition of claim 1, wherein said compound is an ethylene oxide addition product of hexamethylenediamine having an addition mol number of 5.
  14. 15. The developEr composition of claim 1, wherein said compound is an ethylene oxide addition product of trimethylenediamine having an addition mol number of 30.
  15. 16. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of diethylenetriamine having an addition mol number of 50.
  16. 17. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of tetraethylenepentamine having an addition mol number of 50.
  17. 18. The developer composition of claim 1, wherein said compound is a methylene oxide addition product of triethylenetetramine having an addition mol number of 100.
  18. 19. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of diethylenetriamine having an addition mol number of 10.
  19. 20. The developer composition of claim 1, wherein said compound is an ethylene oxide addition product of tetraethylenepentamine having an addition mol number of 10.
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Cited By (10)

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Publication number Priority date Publication date Assignee Title
US3981733A (en) * 1974-07-31 1976-09-21 Polychrome Corporation Silver halide photographic materials containing the addition products of lower alkylene oxides and organic polyamines as anti-fog compounds
US4022621A (en) * 1972-09-01 1977-05-10 Fuji Photo Film Co., Ltd. Photographic developer composition
US4252892A (en) * 1979-12-10 1981-02-24 Eastman Kodak Company Photographic color developer compositions
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties

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GB748745A (en) * 1953-07-01 1956-05-09 Kodak Ltd Light-sensitive silver halide emulsion containing fog inhibiting agents
US3062647A (en) * 1960-04-18 1962-11-06 Eastman Kodak Co Photographic emulsions containing colloidal material and alkylene oxide polymers
US3128183A (en) * 1960-06-17 1964-04-07 Eastman Kodak Co Photographic halide emulsions sensitized with alkylene oxide polymers and aliphatic amines
US3426029A (en) * 1962-06-12 1969-02-04 Eastman Kodak Co Polyfunctional polyalkyleneglycols and their polyquaternary ammonium salts
US3622330A (en) * 1969-12-19 1971-11-23 Du Pont Lithographic developer containing an anionic fatty alcohol sulfate and a nonionic polyethylene oxide surfactant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB748745A (en) * 1953-07-01 1956-05-09 Kodak Ltd Light-sensitive silver halide emulsion containing fog inhibiting agents
US3062647A (en) * 1960-04-18 1962-11-06 Eastman Kodak Co Photographic emulsions containing colloidal material and alkylene oxide polymers
US3128183A (en) * 1960-06-17 1964-04-07 Eastman Kodak Co Photographic halide emulsions sensitized with alkylene oxide polymers and aliphatic amines
US3426029A (en) * 1962-06-12 1969-02-04 Eastman Kodak Co Polyfunctional polyalkyleneglycols and their polyquaternary ammonium salts
US3622330A (en) * 1969-12-19 1971-11-23 Du Pont Lithographic developer containing an anionic fatty alcohol sulfate and a nonionic polyethylene oxide surfactant

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4022621A (en) * 1972-09-01 1977-05-10 Fuji Photo Film Co., Ltd. Photographic developer composition
US3981733A (en) * 1974-07-31 1976-09-21 Polychrome Corporation Silver halide photographic materials containing the addition products of lower alkylene oxides and organic polyamines as anti-fog compounds
US4252892A (en) * 1979-12-10 1981-02-24 Eastman Kodak Company Photographic color developer compositions
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
US4548744A (en) * 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions

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