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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/835—Macromolecular substances therefor, e.g. mordants
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/142—Dye mordant

Definitions

• the invention relates to a solid dye preparation for the production of colored layers, in particular in photographic recording materials.
• Photographic recording materials often contain colored layers. So it is common to provide the back of roll and sheet films with colored gelatin layers. These layers are not only intended to reduce the curling tendency of the film, but also to absorb as completely as possible the radiation which is not absorbed by the emulsion layers during exposure in order to prevent light scattering within the layers and thus the formation of a reflection light source. An improvement can still be achieved by arranging the colored layer not directly on the back of the support, but directly below the lowest emulsion layer, so that no backscattering can occur on the film base.
• the filter layers in multi-layer color photographic recording materials are of particular importance, e.g. a yellow filter layer under a blue-sensitive layer, around which the layers underneath, which are sensitive to green or red light, but are inherently sensitive to blue light, are more sensitive to blue light protect. It is also known to improve the sharpness and the green reproduction in the area of strong exposure by arranging a filter layer which contains a green light-absorbing dye between a green-sensitive layer and an underlying red-sensitive layer.
• the dyes used in antihalation or filter layers have to meet a number of requirements. For example, they should have good absorption properties and be completely and irreversibly bleachable in the usual photographic baths. They should also be readily soluble or dispersible so that they can be introduced into the layers in a sufficient concentration, but must be defined in the respective layer in such a way that they cannot diffuse into adjacent emulsion layers.
• the diffusion resistance is also required for the dyes in the layer arranged on the back of the support, since these Layer can also come into close contact with the emulsion layer, for example in the case of rolled-up films or in the case of superimposed flat films. The diffusion resistance of the dyes must also be guaranteed under extreme conditions such as elevated temperature and humidity.
• anionic dyes which are fixed in the layers by means of suitable mordants.
• the invention has for its object to provide a dye preparation with which stable casting solutions for colored, in particular photographic, layers can be produced in a simple manner. It has been found that water-insoluble crosslinked polymer particles, which are swellable with water due to a content of quaternary ammonium or phosphonium groups, react in an aqueous dispersion with water-soluble acid dyes in an ion exchange reaction and also in the absence of auxiliaries such as wetting agents or protective colloids such as Gelatin, dye-containing latices result without agglomeration or coagulation occurring. These dye-containing latexes can be easily processed into an anhydrous, storage-stable form (e.g. powder), from which fine-particle dye-polymer dispersions can be produced if necessary by stirring in water.
• anhydrous, storage-stable form e.g. powder
• the basic carrier consists of crosslinked polymer particles with a particle diameter of less than 1 ⁇ m and a quaternary ammonium or phosphonium group content of at least 2 meq / g.
• Alkyl radicals as rg e in Formula I by R 1, R 2 and R 3 - are assumed are straight or branched and typically have from 1 to to 12 carbon atoms. Examples include methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, dodecyl.
• R 2 and R 3 have the meaning of carbocyclic radicals, these are optionally substituted cycloalkyl, aralkyl or aryl radicals with preferably 5 to 12 carbon atoms, for example cyclopentyl, cyclohexyl, benzyl, p-methylbenzyl, Chlorobenzyl, nitrobenzyl, cyanobenzyl, methoxybenzyl, methoxycarbonylbenzyl, ethylthiobenzyl, phenyl, tolyl.
• Examples of 5- or 6-membered heterocyclic rings completed by two of the radicals R 1 , R 2 and R 3 are, for example, the pyrrolidine, the piperidine and the morpholine ring.
• Those polymers which are obtained from a monomer mixture by one of the customary addition polymerization techniques, for example by emulsion polymerization, are particularly suitable as the preferred carrier polymer can, which contains both those addition-polymerizable monomers (A) that already contain a quaternary ammonium group or are easily quaternizable, as well as those monomers (V) that contain at least two addition-polymerizable groups and. due to their presence by polymerizing incorporation into different (originally separate ) Polymer chains have a cross-linking effect.
• the quaternization or introduction of quaternary groups can also be carried out after the polymerization, for example by treating tertiary amino groups contained in the polymer with an alkylating quaternizing agent or, for example, by including groups in the polymer with active halogen atoms with tertiary amines or phosphines are implemented.
• the monomer mixture can contain further modifying monomers (M).
• Suitable monomers for the production of the units A are those which contain a polymerizable ethylenically unsaturated double bond and which are linked to a quaternary or quaternizable group via a link.
• a group is referred to as quaternizable, which can be converted into a quaternary group by an alkylation reaction.
• Examples of such quaternizable groups are, for example, a halomethyl group bonded to a phenyl group or a tert-aminomethyl group bonded to a phenyl group.
• alkylation in the present context refers to a reaction in which, for example, between the nitrogen atom of a tertiary amine and a carbon atom of an alkyl group (including substituted alkyl groups) is bonded.
• Particularly advantageous monomers for the generation of units V are trivinylcyclohexane, divinylbenzene, Tetraallyloxyethane, 1,4-butylene dimethacrylate. Two or more of the monomers mentioned can also be used side by side for the production of units V of the polymers according to the invention.
• a wide variety of monoethylenically unsaturated monomers copolymerizable with the other monomers can be used to produce the units M.
• Monomers with conjugated ethylenically unsaturated bonds can also be used here.
• these monomers or the polymerized units M produced from them contain no quaternary groups.
• the units V are preferably present at 1.0 to 5.0 mol%, the units M at 0 to 45 mol% and the units A at 40 to 99 mol%.
• the carrier polymers used according to the invention can advantageously be prepared by customary emulsion polymerization processes, for example by emulsion polymerization of a monomer (A) containing mono-ethylenically unsaturated, quaternary or quaternizable groups with a polyunsaturated monomer (V) and a mono-ethylenically unsaturated monomer (M) in the presence of an anionic surface-active compound, for example sodium lauryl sulfate or in the presence of the sodium salt of a sulfonated condensate of an alkylphenol ethylene oxide condensate (for example Alipal, manufacturer General Dyestuff Corp., USA) and the like, and expediently in the presence of a radical generator or radical initiator, for example in the presence of a free radical generator Initiators of the redox type, for example in the presence of potassium persulfate sodium bisulfite; Potassium persulfate Fe; H 2 0 2 -Fe
• the monomer A contains a functional group which can react with a tertiary amine or phosphine to form a quaternary group
• the latex obtained in the polymerization is reacted with a tertiary amine or tertiary phosphine of the following formula IV wherein R 1 , R 2 , R 3 and Q have the meaning given, implemented, advantageously at temperatures from about -20 ° C to about 150 ° C.
• a polymeric microgel latex is obtained.
• the carrier polymers used according to the invention are generally obtained in the form of a latex, from which they can be isolated in solid form as required. They can be easily redispersed in water and have a particle diameter of less than 1 ⁇ m, preferably from 50 to 200 nm. Suitable carrier polymers are described, for example, in DE-OS 2 551 790, DE-OS 2 846 044 and German patent application P 29 41 819.7. According to the last-mentioned patent application, the structural element A has a structure of the following formula V. wherein R 1 , R 2 , R 3 and x ⁇ have the meaning already given and R 4 is hydrogen or alkyl, preferably methyl.
• the dye preparation according to the invention contains at least one acid dye as a further essential constituent.
• dyes which are known to the person skilled in the art as antihalo or filter dyes. These are generally soluble in water and preferably have at least 2 sulfo groups per molecule. They are distinguished by the fact that they have desired spectral properties and can be decolorized when the photographic materials are processed or can be leached out of the layers. Examples of such dyes are listed below.
• the carrier polymers mentioned are stirred in an aqueous dispersion with an aqueous solution of the acid dye.
• the dye is bound to the polymer particle by an ion exchange reaction, which is usually accompanied by a slight increase in the average particle diameter.
• the dye preparation according to the invention can be easily isolated in solid, unlimited storable form by known work-up processes, e.g. in the form of a powder which can be converted into an aqueous dispersion at any time by stirring with water.
• dye preparations which do not require any further additives such as wetting agents or binders for the dispersion and which spontaneously mix with water without the use of dispersing devices such as e.g. Mixed sirens form finely dispersed systems.
• the dye preparations according to the invention can be prepared in a known manner, e.g. can be processed into tablets or capsules or granules by press agglomeration. Binding agents such as gelatin, polyvinylpyrrolidone or carboxymethyl cellulose are used here. Reference is made to "Römpps Chemie-Lexikon", 7th edition, pages 3453 and 3454.
• colored layers in particular filter layers or antihalation layers
• properties are at least equivalent to the colored layers produced from pickling agents and dye using conventional processes.
• the advantages associated with the use of the dye preparation according to the invention lie in simplified storage and the much simpler and trouble-free production of the casting solutions for the colored layers.
• polymer 2 53.8 g of poly (N, N, N-trimethyl-N-4-methacryloylbutenylammonium chloride-co-styrene-co-divinylbenzene) 49/49/2 mol% (polymer 2) are considered to be 12.7% aqueous dispersion mixed with a solution of 1.008 g of dye 12 in 50 ml of water. The resulting dye-polymer dispersion is precipitated by adding 500 ml of acetone, filtered off, washed twice with a little acetone and dried in vacuo to 30 ° C. A red stain dye powder is obtained.
• the particle sizes of the pickling latexes and the dye-pickling latexes according to the invention are listed in Table 1 below. From the increase in particle sizes it can be seen that the dye has reacted with the latex particles in an ion exchange reaction.
• the comparative polymer forms associations with the dye, which after mixing with gelatin cannot be cast into transparent layers.
• the dispersion of the dye preparation according to the invention can be mixed with gelatin and cast into transparent layers.
• the colored layers produced using the dye preparations according to the invention according to Examples 1, 2 and 3 by admixing gelatin solution and casting on a layer support were compared with layers of equal concentration which had been produced using the same mordant-dye combination but by conventional methods as follows .
• An aqueous pickling solution is added in the appropriate amount to 50 ml of a 10% gelatin solution at 40 ° C.
• the mordant solutions are adjusted to a content of 0.22 equivalents of cationic groups / 1000 ml. Clear or milky cloudy solutions are obtained, which are diluted to 100 ml with water.
• the dye layers are soaked in running water for 16 hours and the density is determined before and after soaking.
• the materials are subjected to the following color negative processing:
• the measured color density before washing (A), after washing (B) and after color negative processing (C) is shown in Table 2 below.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1981
  • 1981-03-14 DE DE19813109931 patent/DE3109931A1/de not_active Withdrawn
• 1982
  • 1982-03-03 EP EP82101610A patent/EP0060438B1/fr not_active Expired
  • 1982-03-03 DE DE8282101610T patent/DE3271814D1/de not_active Expired
  • 1982-03-10 JP JP57036717A patent/JPS57161853A/ja active Pending
• 1983
  • 1983-11-02 US US06/547,466 patent/US4459130A/en not_active Expired - Fee Related

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