US3589902A - Photographic developer concentrate - Google Patents

Photographic developer concentrate Download PDF

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Publication number
US3589902A
US3589902A US601305A US3589902DA US3589902A US 3589902 A US3589902 A US 3589902A US 601305 A US601305 A US 601305A US 3589902D A US3589902D A US 3589902DA US 3589902 A US3589902 A US 3589902A
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US
United States
Prior art keywords
developer
water
polyethylene glycol
polymer
concentrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US601305A
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English (en)
Inventor
Wolfgang Himmelmann
Helmut Mader
Heinz Sassmann
Hans Schellenberger
Karl-Otto Meyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
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Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of US3589902A publication Critical patent/US3589902A/en
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Classifications

    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to liquid developer concentrates which comprise two components that are mixed together and diluted with water to produce a photographic developer bath.
  • Photographic developers have already been produced on a commercial scale in the form of developer concentrates.
  • the organic developer substances in combination with agents which protect against oxidation e.g. sulphites, are dissolved in an acid or neu-' tral concentrate while the alkaline inorganic additive, alkalies, water softeners, antifogging agents such as potassium bromide, and development accelerators are dissolved in an alkaline concentrate.
  • Such concentrates have the advantage of avoiding all the problems inherent in the preparation of solutions. Furthermore, one can prepare without weighing the desired quantity of concentrate for a developer bath, ready for use, simply by mixing the two parts of the concentrate and then diluting with water.
  • developer concentrates used in reproduction work with photographic emulsion layers which have a very steep gradation have a much lower utilisation of sensitivity than a developer solution which has been prepared with water alone.
  • a flattening of the gradation curve frequently occurs in developers when solubilising agents are used.
  • the object of the invention is to provide developer concentrates which contain development accelerators that are equal in efficiency to those developers prepared in aqueous solution.
  • watersoluble derivatives of polyethylene glycols or alkyl-ethers of polyethylene glycol which are produced by (1) copolymerisation of polyethylene glycol esters of unsaturated carboxylic acids with vinyl compounds containing carboxylic or sulfonic acid groups or by (2) graft polymerisation of polyethylene glycol or derivatives thereof with olefinically unsaturated carboxylic or sulfonic acids.
  • Copolymers of (a) reaction products of polyethylene glycols or monoalkylether of such glycols with unsaturated polymerisable acid chlorides or acid esters (e.g. with the chlorides or esters of acrylic acid, methacrylic acid, or vinyl sulfonic acid) (b) with polymerisable monomers containing carboxyl or sulfo groups, e.g., monomers such as acrylic acid, methacrylic acid, vinyl sulfonic acid or styrene sulfonic acid.
  • Reaction products of the above mentioned (a) type which are particularly suitable are those of the following formula:
  • R is a hydrogen atom, an alkyl group containing up to 18 C-atoms, preferably up to 5 C-atoms, a phenyl group which may be substituted, an acyl group, in particular an acyl radical which can be derived from an aliphatic carboxylic acid;
  • R is a hydrogen atom or an alkyl group containing up to 3 C-atoms, especially methyl
  • x is an integer from 8 to 200.
  • the graft polymers are prepared by polymerisation of the monomers in the presence of polyethylene glycol or its derivatives, with peroxides or persulphates as catalysts.
  • the copolymers or graft polymers preferably have a molecular weight of 1,000 to 20,000.
  • the proportion by weight of the polyethylene oxide to the polymerised monomers is about 10:1 to 1:10, preferably about 4:1 to 1:3.
  • the polyethylene oxide chain may also contain small quantities of other alkylene oxides such as propylene oxide, trimethylene oxide etc.
  • the polymeric chain containing vinyl groups may also contain units of other monorners in small quantities, especially those which do not impair the solubility in water, such as low vinyl alkyl ethers, e.g. vinyl ether.
  • polyethylene glycol residue is sufliciently large (at least 8 ethylene glycol radicals) cross-linking does not occur and compounds which are readily soluble in water are obtained.
  • the carboxyl or sulpho groups of the compounds of the present invention in comparison with the known development accelerators such as quaternary salts of the corresponding simple polyalkylene oxides are readily soluble and are not precipitated or salted out from concentrates, even at elevated temperatures.
  • copolymers or graft polymers according to the invention are prepared by known methods. The preparation of some polymers is described in detail as follows:
  • POLYMER 2 A polymer similar in nature to Polymer 1, but containing a different polyethylene oxide chain, is obtained when a polyethylene oxide having an average molecular weight of 1000 is used instead of the polyethylene oxide mentioned above.
  • POLYMER 3 A polymer similar in nature to Polymer 1 but with a different polyethylene oxide chain is obtained by using a polyethylene oxide having an average molecular weight of 6000 instead of the polyethylene oxide used in preparing Polymer 1.
  • POLYMER 4 A polymer similar in nature to Polymer l but with a different polyethylene oxide chain is obtained by using a polyethylene oxide having an average molecular Weight of 12,000 instead of the polyethylene oxide used in preparing Polymer 1.
  • POLYMER 5 g. of a mixture of monoalkylethers of dodecaethylene glycol (the alkyl groups contain 16 to 18 C-atoms) having a molecular weight of about 1500 were dissolved in 600 cc. of dry acetone. 7.2 g. of sodium bicarbonate are added to this and then, while the mixture is stirred vigorously 6 g. of acrylic acid chloride are added dropwise. The mixture is stirred at room temperature until it has a pH of 7 (about 6 hours). Some soda may be added if necessary. The salts are then filtered off under suction and the solvent is evaporated in vacuo. The compound may be used without further purification. Polymerisation with acrylic acid (quantitative ratio 1:1):
  • POLYMER 6 4 is concentrated by evaporation to give a viscous residue, and the product is then precipitated by the addition of acetone and triturated many times over with acetone and dried. It is then reprecipitated from a small quantity of water using acetone. Yield 130 g.
  • POLYMER 7 27 g. of methacrylic acid and 20 g. of polyethylene glycol of molecular weight 4000 were dissolved in 100 cc. of water and the mixture adjusted to pH 7 using sodium hydroxide solution. After the addition of 0.5 g. of potassium persulphate in 50 cc. of Water, the mixture was polymerised at 70 C. for about 7 hours. The mixture was cooled and the polymer Was precipitated with methanol. The precipitate was triturated several times with methanol, dried and then reprecipitated from a small quantity of Water with methanol. Yield: 45 g.
  • the development accelerators according to the invention are used in developer concentrates which comprise two components.
  • solution (A) contains a developer substance and a compound which protects against oxidation, e.g. sodium sulphite or formaldehyde bisulphite, usually in an aqueous organic solvent system.
  • the organic solubilising agents for the developer substance are usually alcohols such as methanol, ethanol or propanol, glycols such as ethylene glycol, dior triethylene glycol, glycol ethers such as ethylene glycol monoethylor diethylene glycol monoethyl ether, dioxane, dimethylformamide and tetrahydrofurfuryl alcohol or tetrahydrofuran.
  • Solution (B) contains an aqueous solution of the remaining chemicals required for the preparation of a photographic developer bath ready for use, i.e. alkali such as sodium carbonate, potassium carbonate, borax or sodium or potassiumhydroxide, Water softeners, such as ethylene diamine tetracetic acid and antifog agents such as potassium bromide.
  • alkali such as sodium carbonate, potassium carbonate, borax or sodium or potassiumhydroxide
  • Water softeners such as ethylene diamine tetracetic acid and antifog agents such as potassium bromide.
  • the use of mixtures of the said alkalies is preferably for the sake of increasing the solubility.
  • the accelerators according to the invention are preferably used in concentrates which contain hydroquinone as developer and formaldehyde bisulphite and/ or sodium sulphite as an agent for protection against oxidation. They may, of course, also be used in combination with other known developers such as aminophenol, p-methylaminophenol, p-phenylenediamine etc.
  • the accelerators may be added both to part A and to part B of the concentrate.
  • 0.01 to 2 g. of an accelerator are employed for 500 ml. of 1 part of a concentrate containing 20 to g. of hydroquinone and 80 to 180 g. of an agent protecting against oxidation, or for 80 to 300 g. of bases, in particular chemically different bases.
  • part A and 125 ml. of part B are mixed and made up to a volume of 1 litre with water.
  • Strips of a black-white negative material of ultrasteep gradation (Lith gradation) which have been exposed through a step wedge are developed for 2.4 and then 6 minutes, and fixed and rinsed with water in the usual manner. Images of normal Lith gradation and sensitivity are obtained.
  • a similar developer which does not contain a compound according to the invention has a sensitiivity which is lower by 2 to 3 shutter stops when the development time is 4 minutes.
  • Example 2 A developer concentrate is prepared using the procedure described in Example 1, except that 1 g. of polymer 7 is used instead of the accelerator described therein.
  • the images obtained after working up do not differ in gradation and sensitivity from images developed in a conventional developer prepared only with Water.
  • a 10% solution of copolymer 1 and a solution of polyethylene glycol of molecular weight 4000 are made alkaline by the addition of dilute sodium hydroxide solution. Pure polyethylene glycol separates out as a second phase on heating while the copolymer according to the invention is not precipitated. This improvement in solubility naturally also occurs in the developer concentrates.
  • a process for the production of a developer bath which comprises preparing a first acid or neutral concentrate containing organic developer and agents that protect against oxidation selected from the group consisting of sodium sulfite and formaldehyde dissolved in an aqueous organic solvent, preparing a second concentrate containing alkaline additive selected from the group consisting of alkaline carbonates and hydroxides and borax, ethylene diamine tetraacetic acid as a water softener and potassium bromide as an antifogging agent in suitable concentrations for photographic development in the developer bath, at least one of said concentrates containing a developer accelerator of a polymer product having a molecular weight of 1,000 to 20,000 selected from the group consisting of (1) a copolymer obtained by free radical polymerisation of a vinyl carboxylic acid or a vinyl sulfonic acid in the presence of polyethylene glycol, (2) a copolymer of (a) the esterification product of polyethylene glycol and a vinyl carboxylic acid, and (b) a vinyl

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
US601305A 1965-12-22 1966-12-13 Photographic developer concentrate Expired - Lifetime US3589902A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA0051149 1965-12-22

Publications (1)

Publication Number Publication Date
US3589902A true US3589902A (en) 1971-06-29

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Application Number Title Priority Date Filing Date
US601305A Expired - Lifetime US3589902A (en) 1965-12-22 1966-12-13 Photographic developer concentrate

Country Status (7)

Country Link
US (1) US3589902A (enrdf_load_stackoverflow)
BE (1) BE690928A (enrdf_load_stackoverflow)
CH (1) CH499131A (enrdf_load_stackoverflow)
DE (1) DE1472790A1 (enrdf_load_stackoverflow)
FR (1) FR1510237A (enrdf_load_stackoverflow)
GB (1) GB1144240A (enrdf_load_stackoverflow)
NL (1) NL6616710A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929485A (en) * 1973-07-26 1975-12-30 Fuji Photo Film Co Ltd Dispersion of silver halide developing agent with surface active polymers of maleic acid half esters
US3996054A (en) * 1971-09-24 1976-12-07 Minnesota Mining And Manufacturing Company Color photographic developing solution
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58111032A (ja) * 1981-12-24 1983-07-01 Konishiroku Photo Ind Co Ltd 現像組成物
US5079288A (en) * 1984-11-12 1992-01-07 Imperial Chemical Industries Plc Oral hygiene compositions and polymers active therein
GB2167075A (en) * 1984-11-12 1986-05-21 Ici Plc Treatment of surfaces and compositions for use therefor
NL8501659A (nl) * 1985-06-07 1987-01-02 Chemco Inc Werkwijze voor het bereiden van fotobad-concentraten in brijvorm, werkwijze ter verwerking van dergelijke concentraten tot gebruiksklare fotografische verwerkingsbaden, een voor deze verwerking geschikte inrichting alsmede een tot deze inrichting behorende pompopstelling.
GB2411967A (en) * 2004-03-11 2005-09-14 Eastman Kodak Co Extrudable photoprocessing composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996054A (en) * 1971-09-24 1976-12-07 Minnesota Mining And Manufacturing Company Color photographic developing solution
US3929485A (en) * 1973-07-26 1975-12-30 Fuji Photo Film Co Ltd Dispersion of silver halide developing agent with surface active polymers of maleic acid half esters
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it

Also Published As

Publication number Publication date
NL6616710A (enrdf_load_stackoverflow) 1967-05-25
DE1472790A1 (de) 1969-03-13
BE690928A (enrdf_load_stackoverflow) 1967-06-09
CH499131A (de) 1970-11-15
FR1510237A (fr) 1968-01-19
GB1144240A (en) 1969-03-05

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