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
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
  • G03C1/8155—Organic compounds therefor

Definitions

• R; and R can be hydrogen or up to a four carbon atom alkyl group.
• R can be hydrogen or a halogen.
• An organic solvent having a high boiling point is also present.
• This invention relates to a color photographic lightsensitive material containing ultraviolet absorbing agents, and particularly to a color photographic light-sensitive material containing at least two ultraviolet absorbing compounds selected from Z-aryl benzotriazole derivatives.
• Ultraviolet absorbing agents incorporated into photographic light-sensitive materials must have the following properties.
• Ultraviolet absorbing agents must not color themselves, and their ultraviolet absorptivity should not lower under exposure to light.
• Z-aryl benzotriazole derivatives are excellent ultraviolet absorbing agents. Further, it is known (see U.S. Pat. 3,253,921) that oilsoluble derivatives of said compounds having a long chain alkyl group can be added to the photographic lightsensitive material in the form of a dispersion.
• the compounds having a comparatively low molecular weight which are described in U.S. Pat. 3,004,896 do not have sufficient solubilities in the desired organic solvents having a high boiling point (for example, dibutyl phthalate, tricresyl phosphate, etc.). Accordingly, a large amount of the solvent is required in order to dissolve these compounds, therefore, the amount of gelatin needed for dispersion increases, and consequently, the thickness of the layer of the photographic sensitive materials increases.
• organic solvents having a lower boiling point for example, ethyl acetate
• the solvent mixture is dispersed in an equeous gelating solution and the dispersion is coated as a supersaturated solution (the solution including the ultraviolet absorbing agent in an over-saturated state in the organic solvent having a high boiling point), there is apt to occur crystallization, and consequently the capacity of the gelatin layer is harmed by separation of crystals in the gelatin layer.
• the present invention comprises a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
• N OH R3 l K/ N Br R and R can represent a member selected from the group consisting of a hydrogen atom and an alkyl group having up to four carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom.
• An organic solvent having a high boiling point is also present.
• the material comprises at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of these should contain a dispersion of the ultraviolet absorbing compounds.
• the gelatin layer may contain a dispersion of at least two of the ultraviolet absorbing compounds.
• the gelatin layer can contain a dispersion of at least two ultraviolet absorbing compounds.
• One object of this invention is to provide a color photographic light-sensitive material containing a dispersion of ultraviolet absorbing agents having a comparatively low molecular weight.
• Another object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which absorb ultraviolet rays of 300- 400 m but which do not absorb visible rays of over 420 Ill 1..
• a further object of this invention is to provide a color photographic light-sensitive material containing ultraviolet absorbing agents which do not flow out or discolor during processing, which do not color or deteriorate with respect to ultraviolet absorptivity by exposure, and which do not have any harmful influence upon the photographic light-sensitive material during preparation, storage or processing.
• the objects can be accomplished by the use of a color photographic light-sensitive material containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the following formula, and an organic solvent having a high boiling point:
• the organic solvent having a high boiling point used in this invention are such as those described in 11.8. Pat. 2,322,027.
• the preferred solvents include di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-ocresyl phosphate, diphenyl mono-p-tert-butyl phenyl phosphate, monophenyl di-p-tert butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tert-butylphenyl phosphate, tri-o-phenylphenyl phosphate, di-p-tert-butylphenyl mono (5-tert-butyI-Z-phenylphenyl)phosphate, etc.
• the low boiling organic solvents such as methanol, ethanol, ethyl acetate, butyl acetate, diethylether, dioxane, tetrahydrofuran, acetone, methylethyl ketone, ethylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether may be used as the solvent assistant.
• the material was then rapidly cooled by immersion in ice-water, and was then allowed to stand at 5 C. in a refrigerator. The separation of crystals was thus observed.
• 2-aryl benzotriazole derivatives represented by Formula 1 used as ultraviolet absorbing agents for color photographic lightsensitive material do not crystallize if two or more of said compounds are used together. It is not as effective to use two or more of the Z-aryl bezotriazole derivatives when the mixing ratio of a compound which is the minimum component is less than 5%, or the mixing ratio of the compound which is the maximum component is over Accordingly, when two or more 2-aryl benzotriazole derivatives are used as ultraviolet absorbing agents for photographic light-sensitive materials, the mixing ratio of these compounds is preferably in the range of from 5% to 90%.
• the 2-aryl benzotriazole derivatives may be used in the range of 1-100 mg./ cm. preferably 5-50 mg./ 100 cm. in forming the film.
• EXAMPLE 1 To a baryta-coated paper, a blue-sensitive silver bromide gelatin emulsion layer containing a yellow coupler: 5-(p-octadecycloyl-aminobenzoyl acetamino) isophthalic acid, a gelatin intermediate layer, a green-sensitive silver bromoiodide gelatin emulsion layer containing a magenta coupler: 1-(3-sulfo-4-phenoxyphenyl)-3-heptadecyI-S-pyrazolone, a gelatin intermediate layer, and a redsensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler: N-octadecyl-1-hydroxy-4- sulfo-Z-naphtamide were applied, in the order recited.
• the obtained coating was divided into two samples, to one of which there was applied a dispersion containing ultraviolet absorbing agents produced by the following procedure so as to contain 20 rug/100 cm. of the ultraviolet absorbing agent. To the other there was applied only a gelatin solution for use as a protective layer.
• the dispersion containing ultraviolet absorbing agents was prepared as follows: 30 g. of Compound 1 and 15 g. each of Compounds 2 and 3 were dissolved in a mixture of 80 g. of dibutyl phthalate and 200 g. of butyl acetate by heating. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed using a colloid mill to produce a homogeneous dispersion.
• Sample coatings thus obtained were given exposure to light through blue, green and red step wedges.
• the samples were then developed with a color developer containing N,N diethyl p phenylene-diamine, and then washed with water, fixed, washed with water, bleached, washed with water, hardened, washed with water and dried by state of the art methods.
• the reflection density thereof was measured at three points (0.5, 1.0 and 1.5 reflection density) for each sample before re-exposing to light.
• a decreasing density ratio was calculated by dividing the balance of the density before exposure and the density after exposure by the density before exposure.
• the calculated decrease of density ratio is shown in the following table.
• EXAMPLE 2 Into the color printing paper described in Example 1, a dispersion containing ultraviolet absorbing agents prepared by the following procedure was added (in the amount of 10 mg./100 cm. of the ultraviolet absorbing agents to the uppermost light-sensitive emulsion layer containing a cyan coupler). The uppermost protective layer was formed of gelatin alone. The same examination was carried out as in Example 1.
• the dispersion described above was prepared" as follows: 30 g. of Compound 1, 10 g. of Compound 2, 10 g. of Compound 3 and 10 g. of Compound 4 were dis-solved (by heating) in a mixture of 60 g. of dibutyl phthalate and 100 g. of ethyl acetate. This solution was added to a mixture of 1 kg. of a 10% aqueous solution of gelatin and 100 g. of a 5% aqueous solution of sodium dodecylbenzene sulfonate. The mixture was dispersed with a colloid mill to obtain a homogeneous dispersion.
• the photographic properties of the red-sensitive emulsion layer were not influenced by the addition of Compounds 1, 2, 3 and 4.
• the couplers were used as a solution of dibutyl phthalate.
• a dispersion containing the ultraviolet absorbing agents used in Example 1 was applied in an amount of 30 mg./100 cm. of the ultraviolet absorbing agent. The film was then dried.
• the color film thus obtained was exposed to light through blue, green and red step wedges.
• the exposed film was then developed with a developer containing 4- amino-3-methyl-N,N-diethylaniline, washed with Water, fixed, washed with water, bleached, washed with water, and dried by conventional state of the art methods.
• the sample thus obtained was exposed for 50 hours to a xenon are by facing the second surface of the sample to the source of light.
• a decrease in the ratio of the color density of this sample was compared with that of the sample which did not have the ultraviolet absorbing layer on the second surface.
• the decrease in the ratio of the color density which was calculated by the same method as in Example 1, is shown in the following table.
• the boiling point for the solvent in the most preferred form of the invention should be a minimum of C., under normal atmospheric pressure.
• the solvent is generally present in an amount less than three times the amount of coupler.
• the amount of solvent can vary from this range, and that amounts greater than three times the amount of coupler are operable.
• a color photographic light-Sensitive material which comprises a support, at least one photographic silver halide emulsion layer and at least one hydrophilic colloid layer, at least one of either the emulsion layers or the colloid layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
• R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
• a color photographic light-sensitive material which comprises an opaque film support, at least one photographic silver halide emulsion layer superposed on said support, and an outer gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
• R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
• a color photographic light-sensitive material which comprises a transparent film support, at least one photographic silver halide emulsion layer superposed on said support, and a gelatin layer superposed on the other surface of said support, said gelatin layer containing a dispersion of at least two ultraviolet absorbing compounds selected from those represented by the formula:
• R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group having up to 4 carbon atoms, and R represents a member selected from the group consisting of a hydrogen atom and a halogen atom, and an organic solvent having a high boiling point.
• said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroXy-5-tert-butyl phenyl)benzotri azole, 2-(2'-hydroxy-3,5'-di-tert butyl phenyl)benzotriazole, 2-(2'-hydroXy-3-tert-butyl-5'-methyl
• said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenylphenyl phosphate and di-p-tert-butylphenyl mono(5-tert-butyl-2-phenylphenyl) phosphate.
• said ultraviolet absorbing compounds are members selected from the group consisting of 2-(2'-hydroxy,5-tert-butyl phenyl)benzotriazole, 2 (2'- hydroxy-B,5-di-tert-butyl phenyl)benzotriazole, 2 (2- hydroXy-3-tert-butyl-5'-methyl phenyl) 5 chlorobenzotriazole and
• a color photographic light-sensitive material as claimed in claim 2 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-p-tert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butylphenyl mono(S-tert-butyI-Z-phenyI-phenyl) phosphate.
• said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzy
• a color photographic light-sensitivematerial as claimed in claim 3 wherein said ultraviolet absorbing compounds are members selected from the group consisting of 2- (2-hydroxy-5 -tert-buty1 phenyl benzotriazole, 2- (2'- hydroxy-3',5-di-tert-butyl phenyl) benzotriazole, 2-(2'- hydroxy-3'-tert butyl-5-methyl phenyD-S-chlorobenzotriazole and 2-(2'-hydroxy-3,5-di-tert-butyl phenyl)-5- chlorobenzotriazole.
• a color photographic light-sensitive material as claimed in claim 3 wherein said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzylphthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl monop-tert-butyl phenyl phosphate, monophenyl di-ptert-butyl phenyl phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl di-o-chlorophenyl phosphate, tri-p-tertbutylphenyl phosphate, tri-o-phenyl-phenyl phosphate and di-p-tert-butyl-phenyl mono(S tert-butyI-Z-phenyl-phenyl)-phosphate.
• said organic solvent having a high boiling point is a member selected from the group consisting of di-n-butylphthalate, benzy
• the color photographic light-sensitive material of claim 1 wherein the mixing ratio of said ultraviolet absorbing compounds is in the range of from 5% to 90%.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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Citations (3)

• 1969
  • 1969-03-21 BE BE730255D patent/BE730255A/xx unknown
  • 1969-03-25 US US810343A patent/US3533794A/en not_active Expired - Lifetime
  • 1969-03-25 DE DE19691915118 patent/DE1915118A1/de active Pending
  • 1969-03-25 FR FR696908660A patent/FR2004675B1/fr not_active Expired
  • 1969-03-25 GB GB05626/69A patent/GB1220425A/en not_active Expired

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