EP0321400A2 - Polymerische farbbildende Kuppler - Google Patents

Polymerische farbbildende Kuppler Download PDF

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Publication number
EP0321400A2
EP0321400A2 EP88810834A EP88810834A EP0321400A2 EP 0321400 A2 EP0321400 A2 EP 0321400A2 EP 88810834 A EP88810834 A EP 88810834A EP 88810834 A EP88810834 A EP 88810834A EP 0321400 A2 EP0321400 A2 EP 0321400A2
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EP
European Patent Office
Prior art keywords
polymer
residue
colour
colour coupler
polymer according
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.)
Withdrawn
Application number
EP88810834A
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English (en)
French (fr)
Inventor
John Leslie Cawse
Philip James Harris
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.)
Ilford Imaging UK Ltd
Original Assignee
Ciba Geigy AG
Ilford Ltd
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Publication date
Application filed by Ciba Geigy AG, Ilford Ltd filed Critical Ciba Geigy AG
Publication of EP0321400A2 publication Critical patent/EP0321400A2/de
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • This invention relates to new polymeric colour couplers and to a process for their production.
  • Polymeric colour couplers are finding increasing use in photographic material instead of colour couplers which require to be incorporated in photographic layers dissolved in an oil.
  • the presence of the oil leads to several disadvantages including rendering the layer which comprises it soft and thus liable to mechanical deformation.
  • photographic material in which the colour couplers are present as a polymer latex can be much thinner than material in which the colour couplers are dissolved in oil. This decrease in thickness leads to sharper images being obtained.
  • the end-groups of polymer molecules formed by free radical initiation are generally incapable of determination with any degree of certainty, however it may be expected that at least one of the end-groups may either be an initiator residue or a group formed by disproportionation or chain transfer reactions during the preparation of the polymer of the claimed structure.
  • Initiator residues may generally include those from alkyl or aryl peroxides, azo compounds, peroxydisulphates, peresters and peroxy carbonates, and specific examples may include the following radicals:
  • End-groups formed by disproportionations reactions may be saturated or unsaturated units from M or the initiating agent. Examples of such units may be found in Principles of Polymer Chemistry, Cornell U.p., P.J. Flay, p. 111.
  • R1 is preferably an alkylene chain having from 2 to 6 carbon atoms or is an interupted alkylene chain having from 2 to 6 carbon atoms there being an oxygen atom or an -NH- group in the chain.
  • Suitable five or six membered rings include pyrolidine, piperidine, or morpholine.
  • R1 is hydrogen or methyl.
  • R2 the divalent organic radical may be the residue of a urethane, a urea, a carbonate, an ester, an ether, a ketone or an amide. Preferably however it is a simple amido linkage -C (O) - NH -.
  • R1 is methyl or hydrogen and R2 is -CO-O-, R1 is an alkylene group and R11 and R111 are each methyl groups.
  • R1 is -CH2-CH2-CH2- or-CH2CH2CH2CH2-.
  • anion X is paratoluene sulphonate.
  • the colour coupler portion W of the monomer may comprise ballasting groups or leaving groups for example so that the colour coupler may act as a two equivalent coupler.
  • the residue of a single colour coupler may be present in the polymer or the residue of more colour couplers may be present.
  • residues of a yellow, a cyan and a magenta colour coupler are present a black or blackish dye is formed on colour development.
  • yellow dye forming monomeric colour couplers include couplers of the general formula II:- wherein each of R3, R4, R5 and R6 are hydrogen, halogen, alkoxy, sulphoxy or sulphonamido, R1 and R2 are as defined above, R7 is hydrogen or a leaving group and L1 and L2 are direct linkages or -NH-.
  • linking groups R2 are -CO-NH- and -O-CH2-CH2-NHSO2-
  • one of L1 and L2 is a direct linkage.
  • An example of such a monomer is Monomer B which is used in the Examples which follow.
  • This monomer has the formula III :
  • a further example of a monomer of general formula II which has a leaving group is the monomer of the formula V :-
  • Another class of yellow dye forming monomeric colour couplers have a pivaloyl end group rather than a benzoyl end group.
  • Such colour couplers have the general formulae VI:- where R1, R6 and R7 have the meanings assigned to the above.
  • magenta dye forming monomeric colour couplers examples include couplers of the general formula VIII:- where R1 and R2 are as defined above, R8 is hydrogen or a leaving group and R10, R11 and R12 are each hydrogen, halogen or alkoxy having 1 to 6 carbon atoms.
  • R1 is hydrogen or -CH3
  • R2 is -CO NH-
  • R2 is -CO NH-
  • R2 include -CO NH (CH2) -O-CO-NH where x 2 - 6, where in the above two formulae the phenylene group is optionally substituted.
  • substitution examples include halogen, alkyl and alkoxy.
  • Particularly useful monomers of formula V are those wherein at least two of R10, R11 and R12 are chlorine atoms.
  • R7 and R8 examples include the group -S- R9 where R9 is a long chain alkyl group having over 10 carbon atoms or is a substituted phenyl group having at least one alkyl or alkoxy group. Preferably R9 has from 12 to 20 carbon atoms in the chain.
  • Monomeric magenta colour couplers of formula VIII are described in E.P. 133262.
  • magenta dye forming monomeric colour couplers are those of general formula XII:- wherein R1, R8 and R10 are as defined above and R10 is alkyl, dialkyl amino, optionally substituted phenyl and optionally substituted acylamino.
  • Substituents in the phenyl or acylamino group include alkyl groups having from 2 to 6 carbon atoms and chlorine atoms.
  • couplers may be prepared by reacting magenta colour couplers of the formula XIII : with acryloyl or methacryloyl chloride.
  • Examples of cyan forming monomeric colour couplers include phenol couplers of the general formula XVI :- and of general formula X V : and a naphthol coupler of the general formula XVI : where in the above three formulae R1 is as defined above, R12 is hydrogen or halogen, R14 is hydrogen or a leaving group such as a halogen atom or substituted alkoxy, R13 is hydrogen or alkyl having 1 to 5 carbon atoms, R15 is an alkyl group having 1 to 6 carbon atoms or ac ylamino or arylamino, and R17 is a linking group and y is 0 or 1, and R16 is hydrogen, alkoxy having 1 to 4 carbon atoms or an amino, amido or sulphonamido group.
  • Suitable substituents in the alkoxy group R14 include alkyl sulphonyl and alkylthio.
  • R1 is hydrogen or methyl.
  • linking groups R17 include alkylene chains of 2 to 6 carbon atoms including interrupted alkylene chains and as mentioned above alkyl groups for example
  • Monomeric colour couplers of general formula XVI are described in B.P. 2,133,170.
  • R1 is preferably methyl or hydrogen and R2 is preferably - CO - O - R1 is preferably an alkylene group and most preferably -CH2-CH2- or -CH2-CH2-CH2- R11 and R111 preferably are each methyl groups, X is Cl or Br or preferably is an organic anion such as para-toluene-sulphonate.
  • a particular useful quaternary ammonium residue is derived from dimethylaminoethyl methacrylate and has the formula :-
  • Suitable for component B comonomers include methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, vinyl acetate; hydroxymethyl methacrylate, hydroxypropylmethacrylate; methacrylic acid, acrylic acid, itaconic acid, 2-carboxyethyl acrylate and the salt thereof, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, styrene, N-vinyl pyrrolidone, 1-vinyl imidazole; 4-vinylpyridine, dimethylaminoethyl methacrylate, vinyl sulphonic acid and the salts thereof, acrylonitrile and vinylidene chloride.
  • a process for the production of a polymer of formula I which comprises dissolving in a water-miscible organic solvent a monomeric colour coupler, a monomer which comprises the quaternary ammonium group and optionally another monomer in the ratio a, b and c as hereinbefore set forth, heating the solution and adding a solution of free radical polymerisation initiating agent and precipitating the polymer by addition of a water immiscible organic solvent.
  • the resultant polymer is water soluble. It is compatible with gelatin and when added to a silver halide emulsion yields a clear dry coating.
  • the polymer is layer substantive and thus when the polymer is incorporated in a gelatino silver halide emulsion and after exposure and colour development a coloured dye image is obtained in the layer in which the polymer is coated.
  • a method of preparing colour photographic material which comprises forming a colour coupler polymer as just described, mixing this polymer with an aqueous gelatino silver halide emulsion and coating the emulsion on a photographic base.
  • Such photographic material may comprise one gelatino silver halide emulsion layer comprising a colour coupler polymer of the present invention, two such silver halide emulsion layers or three such layers.
  • the three layers will most likely be a silver halide layer in which the polymeric colour coupler yields a yellow dye, a layer in which the polymeric colour coupler yields a cyan dye and a layer in which the polymeric colour coupler yields a magenta dye.
  • the colour coupler polymer of the present invention may comprise the residue of a monomeric yellow colour coupler, the residue of a monomeric magenta colour coupler and the residue of a monomeric cyan colour coupler.
  • Polymeric colour couplers of this type are of particular use in monochrome camera speed silver halide material.
  • the photographic material after imagewise exposure is developed in a colour developing bath by use of a para - phenylene diamine developing agent to yield a developed silver image and black dye image.
  • the material is then subjected to a bleach fix treatment which removes the developed silver image and the unexposed silver halide leaving the black dye negative image which can be used to print all types of black and white paper including variable contrast paper.
  • the colour former of this type can also be used to prepare monochrome paper. That is to say paper which can be processed using colour processing chemistry to yield a black dye image instead of a silver image. Paper of this type is of particular use from which to prepare proof prints.
  • the colour former of this type can also be used to reinforce silver halide images at such time that, as occurred some years ago, the price of silver becomes too prohibitive to use in photography when a very dense silver image is required.
  • the photographic material of the present invention preferably comprises gelatin as the binder in the silver halide emulsion layer.
  • the halide used can be any of the silver halides normally used in photography e.g. silver bromide, silver iodobromide, silver chloride, silver chlorobromide and silver iodochlorobromide.
  • the silver halide grains may be both optically and chemically sensitised.
  • the silver halide emulsion may contain stabilisers bactericides and any of the other additives commonly found in photographic silver halide emulsions.
  • the gelatin may have been hardened and may contain coating aids as usual when preparing coated silver halide emulsions.
  • the base can be any of the usual transparent bases used in photography for example subbed polyester, polycarbonate or polystyrene base, or may be a cellulose triacetate or cellulose acetate - butyrate base. If the material is to be used for proof prints the base may be any opaque base in common use for photographic print material for example baryta coated paper base or polyethylene laminated paper base.
  • Para-toluene sulphonic acid (1g) was dissolved in 5cm3 of industrial alcohol. Sufficient of the monomer dimethyl aminoethyl methacrylate was added with stirring to raise the pH to 7. This required 1.3 g.
  • This solution was placed in a 25 cc round bottom flask to which 0.5 g of a monomeric colour coupler was added. The flask was fitted with a magnetic stirrer, condenser and nitrogen inlet. The flask was immersed in an oil bath at 75°C and nitrogen was bubbled through. A solution of azobisisobutyronitrile in industrial alcohol (1.2 cm3 of a 1% solution) was added.
  • This photographic material was then exposed to a white light source for 10 seconds and processed in a colour developing solution for 3.25 minutes at 38°C.
  • the photographic material was then passed to a bleach bath for 6.5 minutes at 35°C.
  • the formula of the bleach bath used is as follows :- ammonium bromide 150 g ferric EDTA 1.8 M 150 ml sodium nitrate 20 g water to 1 litre
  • the material was then washed for 3 minutes in water at 30°C and then dried.
  • p-Toluene sulphonic acid (4 g) was dissolved in industrial alcohol (30 cm3). Sufficient of the monomer dimethyl-aminoethyl methacrylate was added with stirring to raise the pH to 7. This required 5.2 g.
  • This solution was placed in a 50 cm3 flask to which were added 1 g of Monomer A (the magenta monomer), 0.5 g Monomer B (the yellow monomer) and 0.5 g of Monomer C (the cyan monomer).
  • the flask was equipped with a condenser, nitrogen inlet, oil bath and magnetic stirrer. Nitrogen was bubbled through the solution for 10 minutes at room temperature. The flask was then heated at 70°C and maintained at that temperature.
  • a free radical initiator solution was prepared which comprised 0.5 g azobis(isobutyronitrile) in 50 cm3 of industrial alcohol. 4.8 cm3 of this solution was added to the flask. After 2 hours a further 1.2 cm3 of the initiator solution was added and this was repeated after a further 2 hours. After 7 hours reaction time the contents of the flask were added to ether (500 cm3) and a tacky brown solid precipitated. This solid was dissolved in industrial alcohol and reprecipitated in ether to give a free flowing white powder. Yield 7.13 g (67.3 %). The powder was found to be completely water soluble.
  • Example 1 0.1 g of this solid was then added to a similar emulsion as used in Example 1, and the emulsion was coated as in Example 1. A clear glossy coating was found on inspection in green light. As in Example 1 the coating was exposed to white light for 10 seconds and then was processed as set forth in Example 1.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88810834A 1987-12-15 1988-12-06 Polymerische farbbildende Kuppler Withdrawn EP0321400A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8729198 1987-12-15
GB878729198A GB8729198D0 (en) 1987-12-15 1987-12-15 Polymeric colour couplers

Publications (1)

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EP0321400A2 true EP0321400A2 (de) 1989-06-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112708019A (zh) * 2019-10-25 2021-04-27 乐凯化学材料有限公司 一种彩色相纸用水溶性色稳定剂及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112708019A (zh) * 2019-10-25 2021-04-27 乐凯化学材料有限公司 一种彩色相纸用水溶性色稳定剂及其制备方法
CN112708019B (zh) * 2019-10-25 2024-04-30 乐凯化学材料有限公司 一种彩色相纸用水溶性色稳定剂及其制备方法

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Publication number Publication date
GB8729198D0 (en) 1988-01-27

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