US3352681A - Color photographic light-sensitive element containing ultraviolet absorber - Google Patents

Color photographic light-sensitive element containing ultraviolet absorber Download PDF

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Publication number
US3352681A
US3352681A US578444A US57844466A US3352681A US 3352681 A US3352681 A US 3352681A US 578444 A US578444 A US 578444A US 57844466 A US57844466 A US 57844466A US 3352681 A US3352681 A US 3352681A
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Prior art keywords
compound
layer
ultraviolet absorber
sensitive element
photographic light
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Expired - Lifetime
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US578444A
Inventor
Ohi Reiichi
Shirasu Kazuo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/76—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

  • the present invention relates to color photography and more particularly to a color photographic light-sensitive element containing an ultraviolet absorber.
  • a color photographic image is generally inferior in light fastness to a black and white photographic image since the former is composed of dyes formed by color developments. It is natural to attempt to remove this drawback by eliminating ultraviolet rays having a large role in destroying the dyes by utilizing an ultraviolet absorber, and as a practical manner for using such an ultra violet absorber there have generally been adopted the following two methods.
  • a print or a transparent positive picture is, after development, coated or impregnated with an ultraviolet absorber while in the other method an ultraviolet absorber is preliminarily incorporated in a light-sensitive element at the production thereof such that the ultraviolet absorber is not washed out at development processing. From the users convenience the latter method is preferable and the instant invention is also concerned with the latter type.
  • the ultraviolet absorber to be employed for the purpose must be provided with the following properties:
  • the ultraviolet absorber itself is not colored and the ultraviolet absorbing power thereof is not reduced by light exposure.
  • ultraviolet absorbers various compounds have been known as ultraviolet absorbers, but a few of them satisfy the abovementioned four factors, that is, many ofjthe conventionally available ultraviolet absorbers are washed out during development. Several types of ultraviolet absorbers also atfect adversely the photographic characteristics of light-sensitive emulsions.
  • silver halide particles that is, a light-sensitive silver halide layer or may be an intermediate layer or a protective layer containing no silver halide particles; Further, in
  • the compound which will be exposed from the back side of the element, that is, from the support side as a transparent positive picture, the compound may be effectively incorporated in a subbing layer or a coating layer on the back side of the support. Moreover, if necessary, the compound in this invention may be incorporated in more than two coating layers. As these coating layers, a gelatin layer is most suitable, but the layer may contain other high molecular materials.
  • the compound of this invention is superior to the a spectral distribution of energy and intensity simlar to those of a sun beam.
  • the compound used in this invention is excellent as the ultraviolet absorber for color photographic light-sensitive elements.
  • the dispersion was applied to a transparent film base of triacetyl cellulose and dried. From the thus prepared film, the extent of the washing-out of the com-.
  • the preferable photographic properties of the photographic light-sensitive element are not reduced.
  • Example 1 A blue-sensitive silver, iodo-bromide emulsion containing a yellow coupler, 3,S-dicarboXy-a-(4-stearoylamidobenzoyl)acetanilide was applied to baryta paper.
  • the xenon tester used in this experiment is a light source having FADING PERCENTAGE ,OF COLOR IMAGE,
  • the ultraviolet absorber of this invention was incorporated in the intermediate layer between the first light-sensitive emulsion layer and the second light-sensitive emulsion layer instead of incorporating it in the protective layer, the fading of color images formed in the light-sensitive layers under the intermediate layer containing the ultraviolet absorber was prevented as anticipated. Further, almost the same results were obtained when a film base was used as the support instead of the 'baryta paper.
  • Example 2 The dispersion of the compound the same as in Example l was added in the first emulsion layer in Example 1, that is, in the red-sensitive silver chlorobromide emulsion layer.
  • the content of the compound was 5 mg./100 sq. cm.
  • the magenta layer of the second emulsion layer and the yellow layer of the third emulsion layer were as in Example 1.
  • the thus prepared multi-Iayer color photographic lightsensitive element was exposed and subjected to develop- :ment, water-washing, fixing, water-washing, bleach-fixing, water-washing, hardening, water-washing, and drying. Thereafter, the thus processed element was exposed to a xenon tester for 20 hours and the reduction in percentage of color image density was measured, the results of which are shown in the following table:
  • the ultraviolet absorber was incorporated in a photographic light-sensitive emulsion layer
  • the photographic properties of the photographic light-sensitive emulsion was not infected by the compound.
  • a color photographic light-sensitive element having incorporated in at least one layer of photographic lightsensitive emulsion layers, intermediate layers, protective layers, subbing layer and backing layer of a support a compound represented by the general formula wherein R represents an alkyl group having from 8 to 18 carbon atoms.

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Description

United States Patent Ofifice 3,352,681 COLQR PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENT CONTAINING ULTRAVIOLET ABSGRBER Reiichi Chi and Kazuo Shirasu, Ashigara-Karnigun, Kanagawa, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Ashigara-Kamigun, Kanagawa, Japan No Drawing. Filed Sept. 12, 1966, Ser. No. 578,444 Claims priority, application Japan, Sept. 13, 1965,
40/ 55,636 flaims. (Cl. 9684) The present invention relates to color photography and more particularly to a color photographic light-sensitive element containing an ultraviolet absorber.
A color photographic image is generally inferior in light fastness to a black and white photographic image since the former is composed of dyes formed by color developments. It is natural to attempt to remove this drawback by eliminating ultraviolet rays having a large role in destroying the dyes by utilizing an ultraviolet absorber, and as a practical manner for using such an ultra violet absorber there have generally been adopted the following two methods. In the one method, a print or a transparent positive picture is, after development, coated or impregnated with an ultraviolet absorber while in the other method an ultraviolet absorber is preliminarily incorporated in a light-sensitive element at the production thereof such that the ultraviolet absorber is not washed out at development processing. From the users convenience the latter method is preferable and the instant invention is also concerned with the latter type.
The ultraviolet absorber to be employed for the purpose must be provided with the following properties:
(1) It absorbs effectively ultraviolet rays of 300-400 m in wave length but does not absorb visible rays of longer than 420 mu.
(2) It is not washed out or discolored by development processing.
(3) The ultraviolet absorber itself is not colored and the ultraviolet absorbing power thereof is not reduced by light exposure.
(4) It does not give a bad influence on the photographic light-sensitive element containing it at the preparation thereof, during preservation and at development.
Hitherto, various compounds have been known as ultraviolet absorbers, but a few of them satisfy the abovementioned four factors, that is, many ofjthe conventionally available ultraviolet absorbers are washed out during development. Several types of ultraviolet absorbers also atfect adversely the photographic characteristics of light-sensitive emulsions.
The inventors have found that the above-mentioned factors are satisfied When the 2-phenylimino-3-alkyl-5- pyridylmethylene thiazolidone compound shown by the general formula.
silver halide particles, that is, a light-sensitive silver halide layer or may be an intermediate layer or a protective layer containing no silver halide particles; Further, in
Patented Npv. 14, 1967 the light-sensitive element which will be exposed from the back side of the element, that is, from the support side as a transparent positive picture, the compound may be effectively incorporated in a subbing layer or a coating layer on the back side of the support. Moreover, if necessary, the compound in this invention may be incorporated in more than two coating layers. As these coating layers, a gelatin layer is most suitable, but the layer may contain other high molecular materials.
The typical examples of the compound included in the above-mentioned general formula to be used in this invention are shown below but it should be understood that the compounds to be used in this invention as ultraviolet absorbers should not be limited to these.
Compound 1 CH3(CH2)1TN C=O M.P. 6768 C., A max. 329 mu, e: 2.69 10 Compound 2 CHs(CH2) 5N 0:0
M.P. 71-72 C., A max. 329 m 62 216x10 CH3(CH2)15-NO=0 Compound 3 /C=CH \N% M.P. 107108 C., A max. 341 m e: 228x10 Compound 4 CH3(CHZ)13N C=O M.P. 57-58 C., A max. 329 m e2 201x10 Compound 5 CH (OH2)11-N C=O M.P. 66 C., A max. 329 my, 62 216x10 and Compound 6 I GzHs CHa(CH2)a-( JHCH2-N C=O I elemental analysis about carbon, hydrogen and nitrogen almost coincide with the theoretical values. The values of )t max. and e are ones measured in ethanol solution.
The use of a compound similar to the compound of this invention, that is, the use of 2-phenylimino-3-alkyl-5- benzalthiazolidone is disclosed in US. Patent 2,739,888,.
but the compound of this invention is superior to the a spectral distribution of energy and intensity simlar to those of a sun beam.
DECOMPOSITION PERCENTAGE Compound Comp. Comp. Comp. Comp. Comp. Comp. Known 1 2 3 4 5 6 comp.
Percentage known compound in fastness to light. That is, as will be clear from the. experimental results shown below, only 510% of the. compound used in the present invention is decomposed under the same conditions by which 30% of the prior art compound is decomposed. It is a veryimportant factor that an ultraviolet absorber itself is stable to light exposure for a long period of time and hence the compound used in this invention can be considered to have novelty and utility.
It has been confirmed by the following experiment that the compound used in this invention is excellent as the ultraviolet absorber for color photographic light-sensitive elements.
Fifty grams. of any of above-illustrated Compounds 1-6 or the known ultraviolet absorber, 2-phenylimino-3- cetyl-S-benzalthiazolidone was added in 50 got dibutyl phthalate at a temperature not higher than 80 C. and the resulting solution was dispersed in a mixed solution of 1 kg. of a 10% gelatin solution and 100 g. of a 5% solution of sodium alkyl-benzene sulfonate in a colloid mill for minutes, whereby a uniform dispersion of the ultraviolet absorber having an average particle size of about 0.3 micron was obtained.
Thereafter, the dispersion was applied to a transparent film base of triacetyl cellulose and dried. From the thus prepared film, the extent of the washing-out of the com-.
pound was detected. The results are as follows:
layers but 14-0 mg, in particular, 3-2O mg. per 100 sq. cm. of the area of coating layer is suitable. Furthermore,
by the addition of the compound used in this invention, the preferable photographic properties of the photographic light-sensitive element are not reduced.
Example 1 A blue-sensitive silver, iodo-bromide emulsion containing a yellow coupler, 3,S-dicarboXy-a-(4-stearoylamidobenzoyl)acetanilide was applied to baryta paper. The
coupled had been added in the emulsion as an alkaline aqueous solution thereof. Thereafter, a green-sensitive silver chloro-bromide emulsion containing a magenta coupler, l (3-sulfo-3-phenoxyphenyl)-3-stearoyl-5-pyrazolone was applied to the thus formed emulsion layer and further a red-sensitive chloro-bromide emulsion containmg a cyan coupler, N-n-octadecyl-1-hydroxy-4-sulfo-2- naphthamide was applied on the layer. On the thus formed red-sensitive layer there was further coated a protective Reduction percent in transmission density (370 mp) T'une Comp. Comp. Comp. Comp. Comp. Comp. 1 2 3 4 5 6 Water-washing 30 min- 0 0 0 0 0 0 Do 2 hr 0 0 O 0 0 1 3% Na GO 3 soin 30 min 0 0 O 0 O 0 All photographic processing. 47 min- 1 2 1 2 2 3 From the results, it is clear that the above-mentioned Compounds 1-6 were not dissolved out of the gelatin layers in the photographic processing step and waterwashing, fixing, bleach-fixing, water-washing, hardening, water-washing and drying or the steps of development,
fixing, water-washing, bleaching, water-washing,' fixing,
water-washing, hardening, water-washing, and drying.
Then, these samples were exposed to a xenon tester for about 20 hours and thereafter the decomposition percentages of the compounds were measured, the results of which are shown in table below. In addition, the xenon tester used in this experiment is a light source having FADING PERCENTAGE ,OF COLOR IMAGE,
Color image None Comp. 1 Comp. 2 Comp. 8 Comp. 4 Comp. 5 Comp. 6,
Cyan, percent- 15 20 23 15 20 23 Magenta, percent- 20 0 2 3 0 2 3 Yellow, pereent- 40 15 18 20 15 18 20 As clear from the experiment, the fading of color image in the case of incorporating no ultraviolet absorbent in the protective layer was prevented or reduced by the use of the ultraviolet absorbent of this invention.
When the ultraviolet absorber of this invention was incorporated in the intermediate layer between the first light-sensitive emulsion layer and the second light-sensitive emulsion layer instead of incorporating it in the protective layer, the fading of color images formed in the light-sensitive layers under the intermediate layer containing the ultraviolet absorber was prevented as anticipated. Further, almost the same results were obtained when a film base was used as the support instead of the 'baryta paper.
Example 2 The dispersion of the compound the same as in Example l was added in the first emulsion layer in Example 1, that is, in the red-sensitive silver chlorobromide emulsion layer. The content of the compound was 5 mg./100 sq. cm. The magenta layer of the second emulsion layer and the yellow layer of the third emulsion layer were as in Example 1.
The thus prepared multi-Iayer color photographic lightsensitive element was exposed and subjected to develop- :ment, water-washing, fixing, water-washing, bleach-fixing, water-washing, hardening, water-washing, and drying. Thereafter, the thus processed element was exposed to a xenon tester for 20 hours and the reduction in percentage of color image density was measured, the results of which are shown in the following table:
FADING PERCENTAGE OF COLOR IMAGE 6. The color photographic light-sensitive element according to claim 1 wherein said compound is 7. The color photographic light-sensitive element according to claim 1 wherein said compound is C=CH As clear from the experimental results the ultraviolet prevention effect could be obtained also in the case of incorporating the dispersion of the compound of this invention directly in a silver halide emulsion.
Further, in the case where the ultraviolet absorber was incorporated in a photographic light-sensitive emulsion layer, the photographic properties of the photographic light-sensitive emulsion was not infected by the compound.
What is claimed is:
1. A color photographic light-sensitive element having incorporated in at least one layer of photographic lightsensitive emulsion layers, intermediate layers, protective layers, subbing layer and backing layer of a support a compound represented by the general formula wherein R represents an alkyl group having from 8 to 18 carbon atoms.
2. The color photographic light-sensitive element according to claim 1 wherein said compound is incorporated in said layer by adding the compound in the coating solu tion for the layer as a solution thereof in a nQH-Volatile solvent.
8. The color photographic light-sensitive element according to claim 1 wherein said compound is 9. The color photographic light-sensitive element according to claim 1 wherein said compound is 10. The color photographic light-sensitive element according to claim 1 wherein said compound is NORMAN G. TORCHIN, Primary Examiner. R. H. SMITH, Assistant Examiner.

Claims (1)

1. A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE ELEMENT HAVING INCORPORATED IN AT LEAST ONE LAYER OF PHOTOGRAPHIC LIGHTSENSITIVE EMULSION LAYERS, INTERMEDIATE LAYERS, PROTECTIVE LAYERS, SUBBING LAYER AND BACKING LAYER OF A SUPPORT A COMPOUND REPRESENTED BY THE GENERAL FORMULA
US578444A 1965-09-13 1966-09-12 Color photographic light-sensitive element containing ultraviolet absorber Expired - Lifetime US3352681A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US5384235A (en) * 1992-07-01 1995-01-24 Eastman Kodak Company Photographic elements incorporating polymeric ultraviolet absorbers
EP0698817A1 (en) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Assortment of silver halide photographic industrial X-ray films and method of processing said assortment
US5561028A (en) * 1994-06-24 1996-10-01 Mitsubishi Paper Mills Limited Silver halide photographic photosensitive material
EP0772088A1 (en) 1991-03-05 1997-05-07 Fuji Photo Film Co., Ltd. Heat-developable diffusion transfer color photographic material
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5766834A (en) * 1996-05-17 1998-06-16 Eastman Kodak Company Photographic element containing ultraviolet absorbing polymer
US5770353A (en) * 1996-06-28 1998-06-23 Eastman Kodak Company Photographic element having improved ferrotyping resistance and surface appearance
US5856078A (en) * 1997-03-12 1999-01-05 Eastman Kodak Company Antihalation undercoat layer with improved adhesion and reduced finishing dirt
US5858633A (en) * 1994-12-21 1999-01-12 Eastman Kodak Company Photographic elements containing 3-alkyl group substituted 2-hydroxyphenylbenzotriazole UV absorbing polymers
US5914223A (en) * 1997-03-12 1999-06-22 Eastman Kodak Company Photographic element with outer layer having improved physical performance
US5919850A (en) * 1997-03-12 1999-07-06 Eastman Kodak Company UV absorbing polymer particle for use in imaging elements
US5948605A (en) * 1996-08-16 1999-09-07 Eastman Kodak Company Ultraviolet ray absorbing polymer latex compositions, method of making same, and imaging elements employing such particles
EP1016537A2 (en) 1998-12-28 2000-07-05 Fuji Photo Film Co., Ltd. Method and apparatus for forming image with plural coating liquids
US6143484A (en) * 1999-05-06 2000-11-07 Eastman Kodak Company Method for stabilizing photographic dispersions in melts containing fine grain silver halide
US20040228986A1 (en) * 2003-03-26 2004-11-18 Tetsuto Miyanishi Interior ornament and indicator panel for vehicle
US20080263994A1 (en) * 2002-11-09 2008-10-30 Don Kain Method and apparatus for protecting a substrate
US9329281B2 (en) 2013-02-28 2016-05-03 Konica Minolta, Inc. Deposition substrate and scintillator panel

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739888A (en) * 1954-03-29 1956-03-27 Eastman Kodak Co Photographic elements containing thiazolidine derivatives
US3178440A (en) * 1960-03-01 1965-04-13 Ciba Ltd New 1:3:4-thiadiazoles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739888A (en) * 1954-03-29 1956-03-27 Eastman Kodak Co Photographic elements containing thiazolidine derivatives
US3178440A (en) * 1960-03-01 1965-04-13 Ciba Ltd New 1:3:4-thiadiazoles

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0772088A1 (en) 1991-03-05 1997-05-07 Fuji Photo Film Co., Ltd. Heat-developable diffusion transfer color photographic material
US5384235A (en) * 1992-07-01 1995-01-24 Eastman Kodak Company Photographic elements incorporating polymeric ultraviolet absorbers
US5561028A (en) * 1994-06-24 1996-10-01 Mitsubishi Paper Mills Limited Silver halide photographic photosensitive material
EP0698817A1 (en) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Assortment of silver halide photographic industrial X-ray films and method of processing said assortment
US5858633A (en) * 1994-12-21 1999-01-12 Eastman Kodak Company Photographic elements containing 3-alkyl group substituted 2-hydroxyphenylbenzotriazole UV absorbing polymers
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5766834A (en) * 1996-05-17 1998-06-16 Eastman Kodak Company Photographic element containing ultraviolet absorbing polymer
US5770353A (en) * 1996-06-28 1998-06-23 Eastman Kodak Company Photographic element having improved ferrotyping resistance and surface appearance
US5948605A (en) * 1996-08-16 1999-09-07 Eastman Kodak Company Ultraviolet ray absorbing polymer latex compositions, method of making same, and imaging elements employing such particles
US5856078A (en) * 1997-03-12 1999-01-05 Eastman Kodak Company Antihalation undercoat layer with improved adhesion and reduced finishing dirt
US5919850A (en) * 1997-03-12 1999-07-06 Eastman Kodak Company UV absorbing polymer particle for use in imaging elements
US5914223A (en) * 1997-03-12 1999-06-22 Eastman Kodak Company Photographic element with outer layer having improved physical performance
US6030699A (en) * 1997-03-12 2000-02-29 Eastman Kodak Company UV absorbing polymer particle for use in imaging elements
EP1016537A2 (en) 1998-12-28 2000-07-05 Fuji Photo Film Co., Ltd. Method and apparatus for forming image with plural coating liquids
US6143484A (en) * 1999-05-06 2000-11-07 Eastman Kodak Company Method for stabilizing photographic dispersions in melts containing fine grain silver halide
US20080263994A1 (en) * 2002-11-09 2008-10-30 Don Kain Method and apparatus for protecting a substrate
US20040228986A1 (en) * 2003-03-26 2004-11-18 Tetsuto Miyanishi Interior ornament and indicator panel for vehicle
US9329281B2 (en) 2013-02-28 2016-05-03 Konica Minolta, Inc. Deposition substrate and scintillator panel
US9739895B2 (en) 2013-02-28 2017-08-22 Konica Minolta, Inc. Deposition substrate and scintillator panel

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GB1121034A (en) 1968-07-24
BE686819A (en) 1967-02-15

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