EP0146337B1 - Elemente mit hydrophilen Schichten die hydrophobe Substanzen in Polymerteilchen enthalten und Verfahren zu deren Herstellung - Google Patents

Elemente mit hydrophilen Schichten die hydrophobe Substanzen in Polymerteilchen enthalten und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0146337B1
EP0146337B1 EP19840308635 EP84308635A EP0146337B1 EP 0146337 B1 EP0146337 B1 EP 0146337B1 EP 19840308635 EP19840308635 EP 19840308635 EP 84308635 A EP84308635 A EP 84308635A EP 0146337 B1 EP0146337 B1 EP 0146337B1
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Prior art keywords
hydrophobe
polymer particles
hydrophilic
particles
monomers
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EP19840308635
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French (fr)
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EP0146337A3 (en
EP0146337A2 (de
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Herbert Dean Remley
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex

Definitions

  • This invention relates to elements, including radiation-sensitive elements (e.g. color photographic elements).
  • radiation-sensitive elements e.g. color photographic elements
  • it relates to such elements having a hydrophilic layer which contains a hydrophobic compound (e.g. optical brightener) uniformly distributed in polymeric particles.
  • This invention also relates to a method of making such elements.
  • hydrophobe hydrophobic compounds
  • non-polymeric compounds such as color-forming couplers, ultraviolet light absorbing materials or optical brighteners
  • hydrophilic binder materials in the manufacture of radiation-sensitive products.
  • One of the simplest of these techniques involves mechanically dispersing the hydrophobe in solid or liquid form in the binder material by passing a blend of the hydrophobe and material several times through a high energy mill. This technique, however, generally produces unsuitable dispersions which are often unstable.
  • U.S. Patent 3,418,127 discloses a method of finely dispersing a fluorescent compound in latex particles by mixing the fluors in polymerizable monomers and emulsion polymerizing the monomers having the fluors therein.
  • the resulting latex purportedly can be coated and dried to form a thin film, preferably over the radiation-sensitive layers of a photographic element.
  • W. German Patent No. 2,509,342 (published September 11,1975) teaches the incorporation of optical brighteners into polymeric particles by dissolving the optical brighteners in polymerizable monomers and emulsion polymerizing the monomers.
  • Emulsion polymerization proceeds in micelles formed by water-soluble surfactant.
  • ком ⁇ онент migrates from monomer droplets through the water phase and into the micelles prior to polymerization.
  • the resulting latex is purportedly mixed with a compatible colloid (e.g. gelatin) and coated either with a photographic emulsion or in a separate layer in a photographic element.
  • a compatible colloid e.g. gelatin
  • Dispersions of particles produced by such emulsion polymerization techniques tend to suffer from agglomeration.
  • the object of the present invention is to provide elements, including radiation-sensitive elements, which comprise polymer particles in substantially crystal- and agglomeration-free hydrophilic layers having a hydrophobe uniformly distributed throughout.
  • this invention provides an element comprising a support having thereon a hydrophilic layer which comprises a hydrophilic composition comprising a hydrophilic binder and water-insoluble polymer particles dispersed therein,
  • the polymer particles have recurring units derived from one or more ethylenically unsaturated polymerizable monomers
  • the element characterized in that the polymer particles are the result of suspension polymerization and comprise from 0.5 to 10 percent, based on total monomer weight, of a hydrophobe uniformly distributed throughout the particles.
  • the elements of this invention are radiation-sensitive elements (e.g. color photographic paper products) having one or more radiation-sensitive layers.
  • This invention also provides a method of making the element described above.
  • the steps of this method comprise:
  • step (b) is performed under conditions sufficient to promote suspension polymerization of the monomers in the suspended droplets and to form polymeric particles having the hydrophobe uniformly distributed throughout the particles.
  • a radiation-sensitive composition is applied over the hydrophilic layer formed in step (d).
  • the present invention avoids the problems encountered with the latex "loading" technique of U.S. Patent 4,203,716 noted above.
  • the polymer particles useful in this invention are made by suspension polymerization, and are distributed in a hydrophilic binder and coated to provide a substantially crystal-free layer, meaning that substantially all (preferably at least 99 percent) of the hydrophobe is distributed within particles of polymer.
  • the hydrophilic layer is also substantially agglomeration-free, meaning very few, if any, of the polymer particles have stuck together or agglomerated. It has also been found that hydrophobes in the elements of this invention are less likely to wander.
  • the hydrophobe useful in the practice of this invention is a compound which is essentially insoluble in distilled water at 25°C.
  • the dissolved concentration of hydrophobe in water under these conditions is less than 0.5 weight percent, based on the weight of the water.
  • Any such hydrophobe can be used in the practice of this invention as long as it can be dissolved or uniformly dispersed in the ethylenically unsaturated polymerizable monomer(s) to be used in making the polymer particles described below.
  • the hydrophobe is soluble in the monomers at a concentration of at least 8 weight percent, based on the total monomer weight.
  • hydrophobes examples include, but are not limited to, photographic dyes; photographic dye-forming couplers; photographic developing agents or other photographic addenda; optical brighteners; ultraviolet light absorbing compounds; and others known to one skilled in the photographic art.
  • Specific photographic addenda which can act as hydrophobes include those compounds used to perform coupling, silver halide development, oxidized developer scavenging, absorb light of certain wavelengths, spectral sensitizing or desensitizing, or diffusion transfer dye image-forming. Examples of such hydrophobes are listed in considerable detail in U.S.
  • Patent 4,203,716 (noted above), and in Research Disclosure, publications 15162 (November, 1976) and 17643 (December, 1978), paragraphs III, IV, VI, VII and VIII (Research Disclosure is published by Kenneth Mason Publications Limited, The Old Harbourmaster's, 8 North Street, Emsworth, Hampshire, P010 7DD, England). Mixtures of hydrophobes can be used if desired.
  • optical brighteners include such classes of compounds as: oxazoles; oxadiazoles, including benzoxazoles; imidazoles, including benzimidazoles; pyrazolines; coumarins; stilbenes; triazines; imidazolones; naphthotriazoles; acetylenes; vinylene compounds; and others known to a skilled worker in the art.
  • Specific examples of such optical brighteners are described in Research Disclosure, publication 17643, paragraph V, noted above, U.S. Patent 3,666,680 (issued May 30, 1972 to Briggs) and W. German OLS 2,509,342 (published September 11, 1975).
  • the amount of hydrophobe in the polymer particles is generally from 0.5 to 10 weight percent, based on total weight of the monomers in which it is dissolved. Preferably, the amount is from 1 to 8 weight percent, based on the total monomer weight.
  • the polymer particles useful in the practice of this invention are composed of water-insoluble homopolymers or copolymers having recurring units derived from one or more ethylenically unsaturated polymerizable monomers. These copolymers can have recurring units derived from two or more of such monomers, preferably one of which is a monomer having crosslinkable moieties in the molecule. Such monomers are described in more detail below.
  • the water-insoluble polymeric particles useful in this invention comprise polymers represented by the structure: wherein ­A­ represents randomly recurring units in the polymer chain derived from one or more vinyl aromatics, vinyl esters, olefins and diolefins, or esters of ⁇ , ⁇ -unsaturated polymerizable carboxylic acids.
  • vinyl aromatics include styrene, a-methylstyrene, p-bromostyrene, o-chlorostyrene, 2- vinylmesitylene, 1-vinylnaphthalene, m- and p-vinyltoluene and 3,4-dichlorostyrene.
  • Useful vinyl esters include, for example, vinyl acetate, vinyl propionate and vinyl butyrate.
  • Examples of useful esters of a,[3-unsaturated polymerizable carboxylic acids include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, methyl a-bromoacrylate, 4-chlorobutyl acrylate, cyclohexyl acrylate, 2-norbornylmethyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, 2-ethoxyethyl methacrylate, 3-chloropropyl acrylate and 2-2-dimethylbutyl acrylate.
  • Useful olefins and diolefins include, for example, ethylene, propylene, 1,3-butadiene, isoprene, chloroprene, cyclopentadiene and 5-methyl-1,3,6-heptatriene.
  • -A- represents randomly recurring units derived from one or more vinyl aromatics, e.g. styrene, or esters of ⁇ - ⁇ -unsaturated polymerizable carboxylic acids, e.g. methyl methacrylate, butyl acrylate and tetrahydrofurfuryl methacrylate.
  • vinyl aromatics e.g. styrene
  • esters of ⁇ - ⁇ -unsaturated polymerizable carboxylic acids e.g. methyl methacrylate, butyl acrylate and tetrahydrofurfuryl methacrylate.
  • -B- represents randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers having one or more anionic moieties, e.g. sulfo, phosphono or carboxy moieties (including alkali metal or ammonium salts thereof). These recurring units contribute to the dispersibility of the polymer particles in hydrophilic binders.
  • Examples of useful monomers having such anionic moieties include 4-acryloyloxybutane-1-sulfonic acid, sodium salt, 3-acryloyloxy-1-methylpropane-1-sulfonic acid, sodium salt, acrylic and methacrylic acids and alkali metal salts thereof, m- and p-styrenesulfonic acid and alkali metal salts thereof, 3-methacryloyloxy- propane-1-sulfonic acid, sodium salt, lithium methacrylate, N-[3-(N-phenylsulfonyl-N-sodiosulfamoyl)-phenyl]acrylamide, N-[2-(N-methylsulfonyl-N-potassiosulfamoyl)ethyl]methacrylamide, ammonium p-styrenesulfonate and 2-acrylamido-2-methylpropanesulfonic acid, sodium salt.
  • -B- represents randomly recurring units derived from one or more monomers having sulfo or carboxy moieties, such as styrenesulfonic acids or alkali metal salts thereof, acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • sulfo or carboxy moieties such as styrenesulfonic acids or alkali metal salts thereof, acrylic acid, methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • -C- represents randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers having crosslinkable moieties. Such units contribute to the water-insolubility of the resulting polymer. They also make the polymer less soluble in organic solvents generally used in coating operations and thereby reduce the tendency of the hydrophobe to wander.
  • These monomers can have two or more ethylenically unsaturated moieties which crosslink during polymerization (e.g. diacrylates or divinylbenzene). Alternatively, they can have moieties which do not react to provide crosslinking during polymerization, but provide crosslinking because of reaction with a hardener or with another moiety on a different monomer.
  • Such monomers include, for example, 2-acetoacetoxyethyl methacrylate, N-(2-acetoacetoxyethyl)acrylamide, N-(2-acetoacetamidoethyl)acrylamide'and 2-aminoethyl methacrylate hydrochloride.
  • Monomers having two or more ethylenically unsaturated sites available for reaction include; for example, diacrylates, dimethacrylates, triacrylates, trimethacrylates or divinyl compounds.
  • examples of such monomers include divinylbenzene, ethylene dimethacrylate, 2,2-dimethyl-1,3-propylene diacrylate, propylidene dimethacrylate, 1,6-hexamethylene diacrylate, phenyl- ethylene dimethacrylate, tetramethylene dimethacrylate, 2,2,2-trichloroethylidene dimethacrylate, ethylenebis(oxyethylene) diacrylate, oxydiethylene diacrylate, ethylidyne trimethacrylate, allyl acrylate, vinyl allyloxyacetate, 1-vinyloxy-2-allyloxyethane, 2-crotonoyloxyethyl methacrylate, diallyl phthalate, triallyl cyanurate, 2-(5-
  • -C- represents randomly recurring units derived from one or more diacrylates or dimethacrylates, e.g. ethylene diacrylate or ethylene dimethacrylate or both.
  • the polymers useful in the practice of this invention can also comprise minor amounts (less than 5 weight percent) of randomly recurring units in the polymer chain derived from one or more ethylenically unsaturated polymerizable monomers other than those described for -A-, -B- or -C- above.
  • these units are present in very small amounts in the polymer chain so as not to deleteriously affect polymer water insolubility or other desirable polymer properties.
  • they can be derived from vinyl amides (e.g.
  • allyl methyl ether allyl phenyl ether, 2-chlorovinyl methyl ether), N-vinylsuccinamide, N-vinylphthalimide, N-vinylpyrazolidinone, and others known to one skilled in the polymer chemistry art.
  • w represents a weight percent of from 75 to 100, and preferably, from 90 to 99 weight percent
  • x represents a weight percent of from 0 to 20, and preferably from 0.5 to 5 weight percent
  • y represents a weight percent of from 0 to 5, preferably from 0.5 to 5 weight percent. All weight percentages are based on total monomer weight.
  • w is generally from 90 to 100 weight percent
  • x is from 0 to 5 weight percent
  • y is from 0 to 5 weight percent.
  • glass transition temperature (Tg) of the polymers useful in the practice of this invention can be varied widely, they generally have a glass transition temperature (Tg) greater than 70°C in order to prevent diffusion of hydrophobe into the coated layers during drying and storage and to improve compatibility with coating addenda.
  • the glass transition temperature can be determined by any convenient method suitable for this purpose. For example, one such method is differential scanning calorimetry as described in Techniques and Methods of Polymer Evaluation, Volume 2, Marcel Dekker, Inc., N.Y., N.Y., 1970.
  • polymers useful in the practice of this invention include:
  • the polymer particles useful in the practice of this invention are prepared by addition polymerization of the monomers in an aqueous suspension. This is commonly known as “suspension polymerization.” It can be carried out in batch, semi-continuous or continuous operations, as is well known in the art.
  • the method of this invention includes dissolving the hydrophobe(s) in solution with the ethylenically unsaturated polymerizable monomers.
  • the monomer solution is then dispersed as fine droplets in water and subjected to conditions sufficient to promote suspension polymerization of the monomers.
  • one or more polymerization initiators to initiate polymerization and promote its completion.
  • At least one of the initiators, if used, is oleophilic and is dissolved in the monomers along with the hydrophobe.
  • Useful oleophilic initiators include azo compounds [such as the VAZOTM initiators commercially available from DuPont, Wilmington, Delaware, e.g.
  • VAZO-64 T "' which is 2,2'-azobis(2-methylpropionitrile), VAZO ⁇ 52 TM which is 2,2'-azobis(2,4-dimethylvaleronitrile), VAZO-33 T "' which is 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) and VAZO-67 T "' which is 2,2'-azobis(2-methylbutanenitrile)], peroxides (such as lauroyl peroxide and benzoyl peroxide), and others known to one skilled in the art.
  • peroxides such as lauroyl peroxide and benzoyl peroxide
  • Water-soluble polymerization initiators can be used in addition to oleophilic initiators as long as there is sufficient oleophilic initiator to initiate the polymerization of the suspended monomer droplets and an insubstantial amount of emulsion polymerization occurs.
  • One or more surface active agents are also often employed in suspension polymerization to aid in keeping the dispersed monomer droplets from clumping together in the aqueous medium.
  • At least one of the surfactants, if used, is oleophilic and is incorporated into the reaction mixture by dissolving it in the monomer(s) along with the hydrophobe.
  • the temperature of the monomers is maintained at greater than room temperature (20-25 0 C), but less than the room temperature at which the monomers undergo spontaneous polymerization (this varies with the monomer(s) and initiators used). Generally, the temperature used for mixing is in the range of from 30 to 45°C.
  • the resulting solution is dispersed in water as fine droplets and subjected to pressure and temperature conditions suitable for polymerization of the monomers in the suspended droplets and formation of small, suspended polymer particles.
  • the monomer solution is generally present in droplet form in this dispersion in a range of from 20 to 50 percent, based on total dispersion weight.
  • the pressure employed in the polymerization is generally only that needed to maintain the reaction mixture in liquid form, and is usually atmospheric pressure.
  • the polymerization temperature is subject to wide variation as it depends upon several variables including the monomers, initiator and weight percent of monomers in the dispersion. However, generally the temperature is in the range of from 20°C to 120°C. The temperature can vary during the polymerization reaction because of the evolution of heat from the reaction itself.
  • the monomer solution can be dispersed in the aqueous medium prior to polymerization in any suitable manner which may depend upon the polymerization technique (batch, continuous or semi-continuous) employed.
  • the solution is dispersed in the aqueous phase by any means which produces high shear sufficient to form very fine droplets containing monomer, hydrophobe and preferably, oleophilic initiator and surfactant.
  • dispersing can be accomplished by mechanical means such as high-speed stirring or vigorous agitation of some manner, or by pumping a monomer-water mixture through a small orifice or high shear mill into a reactor vessel.
  • the resulting polymer is in the form of small particles, the size of which can be varied by changing the dispersing conditions or amount of surfactant.
  • the average particle size is generally in the range of from 0.1 to 20 micrometers, with polymer particles in the range of from 0.4 to 1 micrometer being particularly useful in the preferred embodiment of this invention utilizing optical brighteners as the hydrophobe.
  • the resulting aqueous suspension of polymeric particles can be used directly after polymerization. Water may be removed, if desired, to increase the percent solids of the suspension.
  • hydrophilic binder materials such as they are often called in the art, to form a hydrophilic composition.
  • binders act as peptizers for the polymeric particles to reduce their tendency to settle.
  • Suitable hydrophilic binders include both naturally-occurring substances, such as proteins (e.g. gelatin, gelatin derivatives, cellulose derivatives), polysaccharides (e.g. dextran), gum arabic and synthetic polymeric substances such as water-soluble polymers [e.g. poly(vinyl alcohol), acrylamide polymers, poly(vinyl pyrrolidones)], and others known to one skilled in the art, as described, for example, in Research Disclosure, publication 17643, noted above, paragraph IX.
  • the polymeric particles are present within a binder in an amount of at least 15, and preferably from 20 to 70, percent based on total dry weight of hydrophilic composition. This corresponds to a coating coverage of polymeric particles of at least 20 mg/m 2 of coated surface area. Particles of different polymers containing the same or different hydrophobes can be used in the same hydrophilic composition, if desired.
  • the resulting hydrophilic composition can be purified, if desired, in any suitable manner to remove any unwanted addenda.
  • the described hydrophilic composition can be applied to a suitable substrate, such as a conventional support, using conventional techniques to provide an element having a hydrophilic layer.
  • This element can be nonradiation-sensitive, if desired.
  • Additional compositions can be applied simultaneously or subsequently to form additional layers over or under the hydrophilic layer. It is specifically contemplated to apply these compositions to a support using coating hoppers or other coating apparatus conventionally employed in preparing single or multiple layer radiation-sensitive elements.
  • Useful coating and drying techniques and supports e.g. paper, polymeric films, glass are described, for example, in Research Disclosure, publication 17643, noted above, paragraphs XV and XVII.
  • the hydrophilic layer so formed is substantially crystal- and agglomeration-free.
  • substantially crystal-free and substantially agglomeration-free refer to a layer having substantially no crystals of hydrophobe or agglomerations of polymer particles within the layer.
  • substantially all hydrophobe preferably at least 99 percent
  • less than 5 crystals of hydrophobe can be observed in a 8.9 x 11.4 cm area of the layer containing the hydrophobe as observed at 250x magnification.
  • the hydrophilic compositions described herein are preferably used in radiation-sensitive elements of various types. Generally, the coating coverage of the hydrophilic composition depends upon its use and the type of element it is incorporated into.
  • Radiation-sensitive elements of this invention include, for example, image transfer materials, lithographic materials, physical development materials, radiographic materials, dry development materials, negative- and positive-working color-forming materials (including color films and color photographic papers), black-and-white films and papers. The details of such materials are well known in the art and are described, for example, in Research Disclosure, publication 17643, noted above.
  • the described hydrophilic compositions are useful in multilayer color photographic paper products having a resin-coated photographic paper support and a plurality of color-forming silver halide emulsion layers coated thereon.
  • the hydrophilic compositions can be used in any location in the radiation-sensitive elements of this invention, including within the radiation-sensitive layers themselves. Preferably, however, they are coated as individual hydrophilic layers, above, below or in between radiation-sensitive layers.
  • the hydrophilic composition contains an optical brightener as the hydrophobe and is incorporated between the support and the radiation-sensitive layer(s) to provide an optical brightener layer.
  • a nonradiation-sensitive element of this invention containing an optical brightener hydrophilic layer was prepared in the following manner:
  • Methyl methacrylate (11.5 kg) monomer was added to a 40 I reactor vessel and warmed to 40°C with gentle stirring.
  • Uvitex OSTM (386 g), an optical brightener commercially-available from Ciba-Geigy (located in Ardsley, New York), was added to the stirring monomer until it was completely dissolved.
  • Aerosol OT-100 T "' 230 g
  • an oleophilic surfactant commercially available from American Cyanamid (located in Wayne, New Jersey)
  • 2,2'-azobis(2-methylpropionitrile) polymerization initiator 57.5 g were similarly added to and dissolved in the monomer.
  • stirring in the vessel was increased to 200 rpmin and distilled water (26.8 kg) heated to 50°C was added to the monomer solution.
  • the resulting dispersion was stirred for an additional 10 minutes and then pumped through a commercially-available high shear Manton-Gaulin TM mill at 2850 rpmin using an orifice clearance of 0.01 cm and a flow rate of 1.5 I/min into another 40 I reactor vessel where stirring was set at 40 rpmin and the temperature controlled at 65°C. The time for pumping through the mill was 26 minutes.
  • This high shear dispersing means provided very fine droplets of monomer in the aqueous phase. Polymerization began immediately and was allowed to proceed for 2 hours at 65°C to give a suspension of polymeric particles of 25% solids.
  • hydrophilic composition was kept at 65°C and stirred at 40 rpmin for 1 hour, filtered through a 30 ⁇ m filter at 65°C and chill set at 40°C.
  • the yield of hydrophilic composition was 39 kg.
  • the hydrophilic composition so prepared was coated on a polyethylene-coated paper support to provide an element of this invention having substantially no crystals or agglomerations.
  • a "loaded" latex was prepared according to U.S. Patent 4,203,716 as follows.
  • Distilled water (10.3 kg) was added to a 40 I reaction vessel and agitated at 120 rpmin while heating to 85°C. A nitrogen atmosphere was maintained throughout the preparation.
  • Potassium persulfate initiator 100 g was dissolved in distilled water (2.5 kg) and the resulting solution was added to the reactor vessel along with Triton 770 TM surfactant (125 g, 30% solids).
  • Triton 770 TM surfactant 125 g, 30% solids.
  • sodium hydroxide 190 g was added to distilled water (8.75 kg) while being maintained at 20-25°C.
  • 2-Acrylamido-2-methylpropanesulfonic acid monomer 500 g was added to the head tank with good mixing and the pH of the dispersion was adjusted to 3.3 with sodium hydroxide. Also added to the head tank were potassium persulfate initiator (50 g) dissolved in distilled water (1.25 kg), Triton 770 TM surfactant (125 g, 30% solids), butyl acrylate monomer (3 kg) and tetrahydrofurfuryl methacrylate monomer (6.5 kg). An air mixer was used to emulsify the monomer mixture in the head tank.
  • the sample of "loaded" latex removed prior to gel addition and a sample of the hydrophilic coating composition made with gel were evaluated for crystals and agglomerations by coating the samples on separate glass substrates and drying the coatings to form coated elements. These elements were examined with an optical microscope at 250x magnification using polarized illumination. Table I below lists the elements evaluated and the keeping conditions of each.
  • Element 1 contained many very fine crystals immediately after coating. These crystals became well-formed rectangles and needles after keeping for 4 hours at 60°C as seen in Element 2. These keeping conditions represent melt-hold conditions.
  • Elements 3 and 4 contain a "loaded" latex and a binder. Large numbers of optical brightener crystals were observed in them. The number of crystals increased under conventional melt-hold conditions.
  • the samples of "loaded" latex and hydrophilic composition were also evaluated for agglomerations using electron microscopic techniques. The presence of agglomerations was observed in each sample with the number of agglomerations greater under conventional melt-hold conditions (4 hours at 60°C).
  • An element of the present invention was prepared in the following manner.
  • a suspension of polymeric particles was prepared according to the procedure described in Example 1 (Part A) using tetrahydrofurfuryl methacrylate, n-butyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid as monomers and Uvitex OS TM optical brightener as the hydrophobe.
  • the suspension containing polymer particles was taken from the reaction vessel after which the vessel was cleaned. The suspension was returned to the vessel and the pH was adjusted to 7 with 10% sodium hydroxide at 60°C and 200 rpmin stirring. A sample of the suspension was taken for evaluation as described below. A 10% gelatin solution in water was added to the reaction vessel and stirring was continued for another 15 minutes.
  • the resulting hydrophilic composition was filtered through cheesecloth and chill-set. Little or no coagulum was found in the reaction vessel.
  • the suspension of polymer particles and hydrophilic composition containing same were also evaluated for agglomerations using electron microscopic techniques. Substantially no agglomerations were observed in either the suspension or composition, even after keeping under the melt-hold conditions.
  • An element of this invention containing an optical brightener hydrophilic layer was prepared in the following manner. This example differs from Example 1 in that the polymer of this example is a crosslinked polymer.
  • Methyl methacrylate (1.15 kg), styrene (1.15 kg) and ethylene dimethacrylate (46 g) monomers and Aerosol OT-100" (23 g) surfactant were stirred in a reactor vessel at 30°C until the surfactant was dissolved.
  • Uvitex OB TM (80 g) brightener and 2,2'-azobis(2-methylpropionitrile) (11.5 g) were similarly added to and dissolved in the monomer solution. Once all of the reagents were dissolved in the monomers, stirring in the vessel was increased to 200 rpmin and an aqueous solution of Aerosol A268TM surfactant (46 g in 5.4 I distilled water) was added to the monomer solution.
  • the resulting dispersion was stirred for an additional 5 minutes and then pumped through a commercially-available high shear Manton-Gaulin TM mill at 3800 rpmin using an orifice clearance of 0.01 cm and a flow rate of 1.5 I/min into another reactor vessel where stirring was set at 40 rpmin and the temperature controlled at 70°C. Polymerization proceeded for 20 hours at 70°C to give a suspension of polymeric particles of 30% solids.
  • This suspension was mixed with gelatin to provide a hydrophilic composition as described in Example 1 above.
  • the resulting composition was coated on a resin-coated support to provide an element of this invention.
  • a photographic element of this invention was prepared in the following manner.
  • a polymeric suspension of poly(methyl methacrylate-co-styrene-co-p-styrene sodium sulfonate-co-ethylene dimethacrylate) (48.5:48.5:1:2 weight ratio) particles containing Uvitex OSTM optical brightener was prepared as described in Example 3. This suspension was mixed with gelatin and incorporated as a brightener layer in a color photographic paper product having the following format using conventional coating techniques and materials.
  • Each gelatin-containing layer was hardened with bis(vinylsulfonylmethyl) ether at 1.8% based on the gelatin coverage.
  • a control paper product was similarly prepared except that the brightener layer was omitted.
  • Example 4 These examples are similar to Example 4 except that the polymer particles containing an optical brightener was incorporated in the interlayer between the magenta and yellow dye layers instead of a separate brightener layer.
  • Uvitex OB TM was incorporated in poly(n-butyl acrylate-co-tetrahydrofurfuryl methacrylate-co-2-acrylamido-2-methylpropanesulfonic acid, sodium salt) (30:65:5 weight ratio) particles (Example 5) and poly-(methyl methacrylate-co-ethylene dimethacrylate) (98:2 weight ratio) particles (Example 6) according to the procedure described in Example 3.
  • Example 4 The resulting polymer suspensions were incorporated in the interlayer and elements were prepared as described in Example 4. A control element was also prepared like the control element of Example 4.
  • Example 4 A sample of each element was processed and the yellow D mln level of each measured as described in Example 4. The differences in Control D min and example D min are shown in Table II below. These data indicate the brightening effectiveness of the brightener-containing polymeric particles in the interlayers of the elements.
  • This example illustrates the incorporation of a cyan dye-forming coupler in polymer particles and the use of such particles in a photographic element.
  • the coupler was incorporated into poly(n-butyl methacrylate-co-methacrylic acid) particles in the following manner:
  • n-Butyl methacrylate (114 g), methacrylic acid (36 g), 2-[a-(2,4-di-t-pentylphenoxy)-butyramidol-4,6-dichloro-5-ethylphenol (90 g) and Aerosol OT TM surfactant (7.2 g) were placed in a 1 liter vessel and heated at 50°C under a nitrogen atmosphere until all materials were dissolved. Distilled water (600 g) was placed in a conventional blender, heated to 60°C and the monomer solution was added thereto and mixed at high speed for 5 minutes.
  • the resulting dispersion was added to a 2 liter reaction vessel and heated to 70°C, after which K 2 S 2 O 8 (1.8 g in 10 ml of water) and Na 2 S 2 O 5 (0.72 g in 10 ml of water) were added to the vessel. After two hours of reaction, the resulting suspension was filtered to remove a small amount of coagulum and the filtrate was adjusted to pH 5.5.
  • the polymer particle suspension was then warmed to 50-60 0 C and a 5% solution of gelatin containing 52 g of dry gelatin was gradually added.
  • the resulting hydrophilic composition was stirred for 30 minutes at 50°C.
  • This hydrophilic composition was coated in a photosensitive emulsion layer on a polyethylene-coated paper support.
  • the coating coverages were 0.3 g/m 2 Ag, 2.8 g/m 2 gelatin and 1.24 g/m 2 polymer particles.
  • the gelatin was hardened with bis(vinylsulfonylmethyl) ether at 1.75% based on gelatin weight.
  • the resulting element was exposed for 0.1 s to a 3000°K light source through a Wratten 29 filter and a graduated neutral density tablet, and processed with the Ektaprint TM 2 process described in Example 4. Sensitometric evaluation of the element indicated that it exhibited suitable cyan dye color.
  • each layer other than the optical brightener layer is not critical to the purpose of this example, but are conventional in the photographic chemistry art.
  • the optical brightener layer of the element of this invention contained gelatin as the hydrophilic binder (1.1 g/m 2 ) and particles of poly(n-butyl acrylate-co-tetrahydrofurfuryl methacrylate-co-2-acrylamido-2-methylpropanesulfonic acid, sodium salt) (49:49:2 weight ratio) (1.8 g/m 2 ) containing Uvitex OBTM optical brightener (0.05 g/m 2 ) uniformly dispersed throughout the particles.
  • the optical brightener layer of the Control element contained a "loaded” latex (1.8 g/m 2 ) like that described in Part A of Example 2 of poly(methyl methacrylate-co-styrene-co-ethylene glycol dimethacrylate) (35:60:5 weight ratio) dispersed in gelatin (1.1 g/m 2 ).
  • the latex was "ioaded” with 1 weight percent of Uvitex OSTM optical brightener although not all of the brightener was in latex particles.
  • UV-fluorescence microscopy was used to study the optical brightener wandering in each element.
  • a cross-secton of each element was subjected to fluorescent light at 1000 Ix using an ultraviolet light filter. Considerable wandering of the optical brightener occurred in the Control element. However, little wandering occurred in the element of this invention.

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Claims (13)

1. Element mit einem Träger mit einer darauf aufgetragenen hydrophilen Schicht mit einer hydrophilen Zusammensetzung mit einem hydrophilen Bindemittel und darin dispergierten, in Wasser unlöslichen Polymerteilchen, die wiederkehrende Einheiten aufweisen, die sich von einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren ableiten, dadurch gekennzeichnet, daß die Polymerteilchen das Ergebnis einer Suspensionspolymerisation sind und 0,5 bis 10 Prozent, bezogen auf das Gesamt- monomerengewicht, eines hydrophoben Stoffes, der gleichförmig in den Teilchen verteilt vorliegt, enthalten.
2. Element nach Anspruch 1, das eine strahlungsempfindliche Schicht aufweist.
3. Element nach Anspruch 2, bestehend aus einem mehrschichtigen farbphotographischen Element mit einem Papierträger, auf dem eine Mehrzahl photographischer, farbbildender Silberhalogenidemulsionsschichten angeordnet ist.
4. Element nach einem der Ansprüche 1 bis 3, bei dem der hydrophobe Stoff ein photographischer Farbstoff, ein einen photographischen Farbstoff bildender Kupper, eine photographische Entwicklerverbindung, ein optischer Aufheller oder eine ultraviolettes Licht absorbierende Verbindung ist.
5. Element nach einem der Ansprüche 1 bis 4, in dem der hydrophobe Stoff ein optischer Aufheller ist.
6. Element nach einem der Ansprüche 1 bis 5, in dem die Polymerteilchen wiederkehrende Einheiten aufweisen, die sich von zwei oder mehr ethylenisch ungesättigten polymerisierbaren Monomeren ableiten, wobei mindestens eines von diesen Monomeren einen quervernetzbaren Rest aufweist.
7. Element nach einem der Ansprüche 1 bis 6, in dem die Polymerteilchen aus Polymeren aufgebaut sind, die sich durch die folgende Struktur darstellen lassen:
Figure imgb0010
worin -A- willkürlich verteilte wiederkehrende Einheiten darstellt, die sich ableiten von einer oder mehreren vinylaromatischen Verbindungen, Olefinen und Diolefinen, Vinylestern oder Estern von a,ß- ungesättigten polymerisierbaren Carbonsäuren;
-B- für willkürlich verteilte wiederkehrende Einheiten steht, die sich von einem oder meheren ethylenisch ungesättigten polymerisierbaren Monomeren ableiten, die ein oder mehrere anionische Reste aufweisen;
­C­ willkürlich verteilte wiederkehrende Einheiten darstellt, die sich von einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren ableiten, die einen quervernetzbaren Rest aufweisen; und w für 75 bis 100 Gew.-Prozent; x für 0 bis 20 Gew.-Prozent und y für 0 bis 5 Gew.-Prozent, jeweils auf das Gesamtmonomerengewicht bezogen, stehen.
8. Element nach einem der Ansprüche 2 bis 7, in dem die hydrophile Schicht mit dem Gehalt an Polymerteilchen zwischen dem Träger und der oder den strahlungsempfindlichen Schichten angeordnet ist.
9. Element nach einem der Ansprüche 1 bis 8, in dem der hydrophobe Stoff ein 2,5-Bis(6-butyl-2-benzoxazolyl)-thiophen optischer Aufheller ist, und die Polymerteilchen aus Poly(methylmethacrylat-co- styrol-co-ethylenglycol-dimethacrylat) bestehen.
10. Verfahren zur Herstellung des Elementes gemäß Anspruch 1 mit den Stufen:
(a) Lösen von 0,5 bis 10 Prozent, bezogen auf das Gesamt-Monomerengewicht, eines hydrophoben Stoffes in Lösung mit einem oder mehreren ethylenisch ungesättigten polymerisierbaren Monomeren;
(b) Dispergieren und Polymerisieren der in Stufe (a) gebildeten Lösung in Wasser als feine Tröpfchen;
(c) Dispergieren oder polymeren Teilchen, die in Stufe (b) angefallen sind, in einem hydrophilen Bindemittel unter Bildung einer hydrophilen Zusammensetzung; und
(d) Aufbringen der hydrophilen Zusammensetzung auf einen Träger;
dadurch gekennzeichnet, daß die Stufe (b) unter Bedingungen durchgeführt wird, die ausreichen, um die Suspensionspolymerisation der Monomeren in den Tröpfchen zu fördern und um polymere Teilchen zu bilden, die den hydrophoben Stoff gleichförmig über die Teilchen verteilt enthalten.
11. Verfahren nach Anspruch 10, in dem eine strahlungsempfindliche Zusammensetzung auf die hydrophile Schicht aufgebracht wird.
12. Verfahren nach einem der Ansprüche 10 oder 11, in dem der hydrophobe Stoff ein optischer Aufheller ist.
13. Verfahren nach einem der Ansprüche 10 bis 12, bei dem die Stufe (a) bei einer Temperatur durchgeführt wird, die größer als Raumtemperatur, jedoch geringer als die Temperatur, bei der eine spontane Polymerisation der Monomeren erfolgt, ist.
EP19840308635 1983-12-16 1984-12-12 Elemente mit hydrophilen Schichten die hydrophobe Substanzen in Polymerteilchen enthalten und Verfahren zu deren Herstellung Expired EP0146337B1 (de)

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JPS63503486A (ja) * 1986-05-01 1988-12-15 イーストマン コダック カンパニー 重合体粒子内に疎水性物質を含有する親水性層を有する画像形成素子及びその製造方法
JPS6344658A (ja) * 1986-08-13 1988-02-25 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
EP0256537B1 (de) * 1986-08-15 1992-12-30 Fuji Photo Film Co., Ltd. Farbkopie und Verfahren zu deren Herstellung
JPS63304243A (ja) * 1987-06-04 1988-12-12 Konica Corp ハロゲン化銀写真印画紙の製造方法
JPH0823677B2 (ja) * 1988-01-08 1996-03-06 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
DE69314318T2 (de) * 1993-04-27 1998-04-09 Agfa Gevaert Nv Verfahren zum Einfügen von einer Wasserumlöslichen Verbindung in eine hydrophile Schicht
EP0825484A3 (de) * 1996-08-16 1998-04-01 Eastman Kodak Company Ultraviolettabsorbierende Polymerpartikelzusammensetzungen
EP1955858B1 (de) 2007-02-06 2014-06-18 FUJIFILM Corporation Tintenstrahlaufzeichnungsverfahren und Vorrichtung

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US3491235A (en) * 1964-08-13 1970-01-20 Eastman Kodak Co Organic scintillating layer in a photographic element
JPS50126732A (de) * 1974-03-06 1975-10-06
US4203716A (en) * 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
JPS56126830A (en) * 1980-03-11 1981-10-05 Konishiroku Photo Ind Co Ltd Silver halide photographic sensitive material
JPS60107642A (ja) * 1983-11-16 1985-06-13 Konishiroku Photo Ind Co Ltd 疎水性写真用添加物を親水性バインダ−中に分散させる方法およびハロゲン化銀写真感光材料

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