US3794493A - Photographic layers which contain uv-absorbers - Google Patents

Photographic layers which contain uv-absorbers Download PDF

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Publication number
US3794493A
US3794493A US00154229A US3794493DA US3794493A US 3794493 A US3794493 A US 3794493A US 00154229 A US00154229 A US 00154229A US 3794493D A US3794493D A US 3794493DA US 3794493 A US3794493 A US 3794493A
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United States
Prior art keywords
compounds
layer
absorbent
layers
photographic
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Expired - Lifetime
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US00154229A
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English (en)
Inventor
J Sobel
F Nittel
W Pelz
W Himmelmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication date
Priority claimed from CH931970A external-priority patent/CH529815A/de
Priority claimed from DE19702036719 external-priority patent/DE2036719C3/de
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Application granted granted Critical
Publication of US3794493A publication Critical patent/US3794493A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds

Definitions

  • the UV-absorbing layer contains as UV-absorbent a 2-phenolbenzotriazole, the benzo ring of which is substituted with 2 butyl groups.
  • the invention relates to photographic layers which contain UV-absorbent compounds.
  • UV- absorbent compounds Numerous compounds which absorb light in the UV-region of the spectrum and are, therefore, suitable for the production of UV-filters and UV-protective coatings. Such coatings are used in photographic material for increasing the light fastness of color images.
  • the UV- absorbent compounds should be incorporated in a separate protective layer in as high a concentration as possible in order to achieve the greatest possible effect.
  • the UV-absorbent compounds should be colorless and should have a high coefficient of extinction in the UV-region and should be as stable as possible.
  • the UV-absorbent compounds can be used in many different ways, e.g. in Water insoluble binders. In this case, the finished color image is coated with such a solution in a separate working step. This procedure, however, is only economical for images of large shapes and sizes and is, therefore, not generally applicable. Incorporation of water soluble and water insoluble UV-ab sorbent compounds in a diffusion fast manner in a protective layer has also been described. In this case, the chemical and physical properties of the UV-absorbent compound must meet certain requirements, e.g. it must be possible for the absorbent compound to be used in a highly concentrated form in layers of a thickness of 1 to 2 ,um. without precipitating from the protective layer in the form of crystals or an oil. The UV absorbent compound must, of course, be inert towards photographic processing baths and must not undergo yellowing on exposure to light.
  • UV-absorbent compounds A very wide variety of UV-absorbent compounds have already been described for the present purpose. Many of these compounds, however, do not sufficiently satisfy the requirements in practice. Aromatic azines have, inter alia, been particularly recommended as UV-absorbent compounds, but these generally have a high melting point so that they are diflicult to use because of their tendency to crystallize. Derivatives of this type which can easily be incorporated in photographic layers, which are described in German Pat. No. 1,182,066, are slightly yellowish so that they are detrimental to the white color images. The reason for thls 1s that a slight absorption of light from the visible region of the spectrum occurs.
  • a photographic material with a UV-absorbent layer which contains a UV-absorber of the following formula OH R R in which R and R stand for sec.-butyl or tert.-butyl and R represents hydrogen, alkyl or alkoxy having up to 3 carbon atoms or halogen such as chlorine or bromine. But at least one of the substituents R and R represents sec.- butyl.
  • the phenol ring may also be further substituted e.g. by alkyl or alkoxy having up to 3 carbon atoms or halogen for example chlorine or bromine.
  • Particular utility is exhibited by the following compounds:
  • the compounds to be used according to the invention are prepared in known manner. Preferably one starts from a diazotized o-nitraniline which is coupled with the butyl-substituted phenol to yield the o-nitrophenylazo compounds. The last mentioned compounds are reduced in alkaline medium with zinc dust whereby the benzotriazols are formed.
  • COMPOUND 1 138 g. (1 mol) of o-nitraniline are stirred up with 500 ml. of concentrated aqueous hydrochloric acid, mixed with 750 m1. of water and diazotized with 70 g. (1 mol) sodium nitrite in 150 ml. of water at a temperature of between and C. Thereafter it is stirred for another half hour.
  • the resulting diazonium solution is added quickly drop by drop while stirring at a temperautre of 5 C. to a solution of 206 g. 2-sec.-butyl-4-tert.-butyl-phenol (1 mol), 140 g. of sodium acetate and 400 g. of concentrated (45%) aqueous sodium hydroxide in 2.3 l. of methanol. The mixture is stirred for some hours and left standing over night.
  • the precipitated red dye is filtered off, washed with water and dried (M.P. ca. 80 C.).
  • the raw product is recrystallized from methanol, the precipitate filtered off and washed with cold methanol (M.P. 92-93 C.).
  • the other compounds can be prepared in a similar manner.
  • the UV-absorbent compounds which are to be used according to the invention have exceptionally advantageous absorption properties.
  • the absorption curve drops steeply at the beginning of the visible region of the spectrum.
  • the UV-absorbent compounds are readily soluble in those particular solvents which are used as so-called oil forming agents for the production of color photographic materials.
  • the solution can easily be emulsified in the casting solutions for the layers.
  • UV-absorbent compounds to be used according to the invention may also be used in combination with other UV-absorbent compounds.
  • the UV-absorbent compounds do not deleteriously affect the photographic properties of adjacent layers and in particular the color coupling reaction of dissolved dye derivatives is not reduced. Many of the known UV-absorbent compounds even of the benztriazole series are detrimental in this respect. The molar extinction coefficient is exceptionally high, so that the quantity of 'UV- absorbent compound used can be kept comparatively low.
  • the UV-absorbent compounds are preferably emulsified in the casting solutions for the particular layer in the form of their solutions in high boiling solvents, by using a suitable dispersing apparatus.
  • the proportions in which the UV-absorbent compounds are mixed with the solvents may vary between 1:1 and 1:01.
  • Low boiling auxiliary solvents such as ethyl acetate, methylene chloride, alcohols and mixtures of these solvents may be used. After dispersion, the low boiling solv cuts are removed in thin layer evaporators under vacuum.
  • Suitable water insoluble, high boiling compounds are, for example, dibutyl phthalate, tricresyl phosphate and particularly higher fatty acids, and preferably branched fatty acids having about 10 to 20 C-atoms.
  • the UV-absorbent compounds may be added directly to the silver halide emulsions which contain color couplers or to a gelatin-containing solution of the protective layer.
  • gelatin layers which contain the UV-absorbent compound may be arranged in any position in the various layers of the photographic material, but are preferably positioned above the layers which contain the image dye.
  • the UV-absorbent compounds are particularly suitable as the topmost layer for photographic multi-layered materials of the usual arrangement.
  • the concentration of the UV-absorbent compounds in the layers may vary within wide limits. An addition of 0.1-1.0 parts by weight, per part of the binding agent in the layer, has proved to be sufficient.
  • the binding agent for the UV-absorbing layers of the present invention is preferably gelatine which however can be replaced partially according to a preferred embodiment of the invention by homoor copolymers of acrylic or methacrylic acid esters with aliphatic alcohols having up to 5 carbon atoms.
  • suitable are also anionic or cationic polyurethanes as described in US. patent specifications Nos. 3,374,095 and 3,397,989.
  • the polyurethanes are also applied in combination with gelatine.
  • the binding agents which are used in addition to gelatine are added preferably from an aqueous latex of the polymer.
  • the concentration of the polymer in the layer is preferably 550% based on the total weight of the binding agent.
  • the concentration of the UV-absorbing compounds is so chosen that on exposure to light the stability of the image dyes is equally satisfactory in the three layers.
  • the layer thickness of the protective layers which contain UV-absorbent compounds is preferably 2 to 5 m.
  • the color photographic material is found to be improved by a factor of 4 to 10 compared with the same color photo- 1graphic material which does not contain these protective ayers.
  • the improvement in fastness is determined by exposing both images at the same color density to the same degree of bleaching.
  • the ratio of lux hours required gives a measure of the improvement factor.
  • the improvement factor depends not only on the concentration of the UV-absorbent izompound but also on the thickness of the protective ayer.
  • the layers which contain the UV-absorbent compound are completely transparent in the dry state and practically colorless. They are stable against the photographic processing baths, e.g. a colorforming development bath. No yellowing can be detected after prolonged exposure to lg t.
  • Example 1 On to a paper support which is laminated on both sides with a polyethylene layer containing a white pigment are applied the following layers:
  • a gelatine layer having a thickness of 3 p.111.
  • Another stripe of the above material is coated with a UV-absorbing layer from the following casting emulsion:
  • the UV-absorbing layer has a thickness of 3am.
  • Both samples are processed in identical manner including exposure and color-forming development.
  • the light-fastness of the final image is determined as described above.
  • the improvement factor lies in the range of 4-10 depending on the kind of the color coupler.
  • the UV-absorbing layer does not deleteriously affect the photographic properties of the adjacent emulsion layers or the time of color-forming development. Formation of a uniform dye fog is not observed.
  • Example 2 The same procedure is applied as described in Example 1 but the casting solution for the UV-absorbing layer is not applied as a separate top layer but is added to the blue-sensitive silver halide emulsion layer containingthe yellow color coupler.
  • the casting solution containing the UV-absorbent is changed in so far as 50 g. of the same UV-absorber and 75 g. of the 30% methanolic solution of pentadecylensuccinic acid is used.
  • Example 3 The procedure is the same as described in Example 1 the casting solution for the UV-absorbing layer has the following composition:
  • Example 4 The procedure is the same as described in Example 1.
  • the casting solution for the UV-absorbing layer has the following composition:
  • Example 5 30 g. of the UV-absorber referred to below 3 g. of the bis(2-ethyl)-hexylester of sulfossucinic acid in 60 g. of ethyl acetate.
  • Sample 1 UV-absor-ber Compound 1
  • Sample 2 UV-absorber Compound 2
  • Sample 3 The UV-absorber of the following formula N ⁇ HO N aHnGso) The above samples were stored at 40 C. and in the refrigerator and the behaviour of the emulsions with respect to the precipitation of the UV-absorbing agents is observed. The results are shown in the following table.
  • Digestion Retrigerator Compound 1 hour 6 hours 24 hours 3 days 1 Good Good.--" Good Good. 2.- do do do do Do. A Slightly Orys- Completely Crystalerystallized. tallized. crystallized. lized.
  • Precipitation of the UV-absorber of sample 3 can be reduced by a suificiently high addition of an oil former such as dibutylphthalate or tricresyl phosphate.
  • an oil former such as dibutylphthalate or tricresyl phosphate.
  • the required amount of about 0.5 to 1 part by weight of oil former per part of UV-absorber is however so high that the layers are getting hydrophobic which elfects processing of the exposed color-photographic material.
  • the diffusion of the aqueous processing baths into the photographic layers is made diflicult, which is in particular relevant with hydrophilic color-forming developers such as N-butyl-N- w-sulfobutyl-p-phenylenediamine.
  • a photographic element comprising a support, at least one hydrophilic photographic silver halide emulsion layer and incorporated in one of the hydrophilic layers of said photographic element a UV-absorbing compound of the following formula:
  • UV-absorber is contained in an amount of 0.1-0.5 parts by weight per one part by weight of binding agent of the layer.
  • the finished photographic element comprising a support having thereon a plurality of developed and fixed photographic emulsion layers containing dye images formed upon color-forming development, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing the dye image subject to fading laying between said support and an UV-a'bsorbing layer containing an ultraviolet absorbing compound of the following formula:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00154229A 1970-06-19 1971-06-17 Photographic layers which contain uv-absorbers Expired - Lifetime US3794493A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH931970A CH529815A (de) 1970-06-19 1970-06-19 Verwendung von 2-(2'Hydroxyphenyl)-benztriazolverbindungen als Lichtschutzmittel
DE19702036719 DE2036719C3 (de) 1970-07-24 1970-07-24 Photographisches Material

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US3794493A true US3794493A (en) 1974-02-26

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JP (1) JPS5512587B1 (enrdf_load_stackoverflow)
CA (1) CA1018813A (enrdf_load_stackoverflow)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009038A (en) * 1974-05-23 1977-02-22 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
US4126460A (en) * 1975-08-28 1978-11-21 Fuji Photo Film Co., Ltd. Light sensitive printing plate comprising a matted overlayer
US4486518A (en) * 1981-02-20 1984-12-04 Polychrome Corporation Duplicating film mask with radiation absorbing benzophenone in processed positive-working radiation sensitive layer on transparent substrate
US4518686A (en) * 1982-06-05 1985-05-21 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
US4540656A (en) * 1982-06-01 1985-09-10 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material
US4968704A (en) * 1988-08-13 1990-11-06 Pfizer Inc. Pyridine compounds which are useful as anti-arrhythmic agents
US5097041A (en) * 1989-10-19 1992-03-17 Ciba-Geigy Corporation Purification of 2-aryl-2h-benzotriazoles
US5370988A (en) * 1994-02-28 1994-12-06 Minnesota Mining And Manufacturing Company Print stabilizers and antifoggants for photothermography
US5772920A (en) * 1995-07-12 1998-06-30 Clariant Finance (Bvi) Limited U.V. absorber compositions
US5945136A (en) * 1997-04-03 1999-08-31 Technophar Equipment & Service Limited Heating elevator for capsule making machine
US6000928A (en) * 1997-04-03 1999-12-14 Technophar Equipment & Service Limited Capsule making machine having improved pin bars and air flow characteristics
USRE37693E1 (en) * 1982-06-05 2002-05-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005289916A (ja) * 2004-04-01 2005-10-20 Shiseido Co Ltd 紫外線吸収剤及びこれを含有する皮膚外用剤
US8119562B2 (en) 2007-03-29 2012-02-21 Fujifilm Corporation Heat-sensitive transfer sheet and image-forming method using heat-sensitive transfer system

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009038A (en) * 1974-05-23 1977-02-22 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
US4126460A (en) * 1975-08-28 1978-11-21 Fuji Photo Film Co., Ltd. Light sensitive printing plate comprising a matted overlayer
US4486518A (en) * 1981-02-20 1984-12-04 Polychrome Corporation Duplicating film mask with radiation absorbing benzophenone in processed positive-working radiation sensitive layer on transparent substrate
US4540656A (en) * 1982-06-01 1985-09-10 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material
US4518686A (en) * 1982-06-05 1985-05-21 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
USRE37693E1 (en) * 1982-06-05 2002-05-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
US4968704A (en) * 1988-08-13 1990-11-06 Pfizer Inc. Pyridine compounds which are useful as anti-arrhythmic agents
US5097041A (en) * 1989-10-19 1992-03-17 Ciba-Geigy Corporation Purification of 2-aryl-2h-benzotriazoles
US5370988A (en) * 1994-02-28 1994-12-06 Minnesota Mining And Manufacturing Company Print stabilizers and antifoggants for photothermography
US5772920A (en) * 1995-07-12 1998-06-30 Clariant Finance (Bvi) Limited U.V. absorber compositions
US5945136A (en) * 1997-04-03 1999-08-31 Technophar Equipment & Service Limited Heating elevator for capsule making machine
US6000928A (en) * 1997-04-03 1999-12-14 Technophar Equipment & Service Limited Capsule making machine having improved pin bars and air flow characteristics

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Publication number Publication date
JPS5512587B1 (enrdf_load_stackoverflow) 1980-04-02
CA1018813A (en) 1977-10-11

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