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Publication numberUS3352681 A
Publication typeGrant
Publication dateNov 14, 1967
Filing dateSep 12, 1966
Priority dateSep 13, 1965
Also published asDE1547853A1
Publication numberUS 3352681 A, US 3352681A, US-A-3352681, US3352681 A, US3352681A
InventorsKazuo Shirasu, Reiichi Ohi
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Color photographic light-sensitive element containing ultraviolet absorber
US 3352681 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

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.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2739888 *Mar 29, 1954Mar 27, 1956Eastman Kodak CoPhotographic elements containing thiazolidine derivatives
US3178440 *Feb 28, 1961Apr 13, 1965Ciba LtdNew 1:3:4-thiadiazoles
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5384235 *Jul 1, 1992Jan 24, 1995Eastman Kodak CompanyPhotographic elements incorporating polymeric ultraviolet absorbers
US5561028 *Jun 2, 1995Oct 1, 1996Mitsubishi Paper Mills LimitedSilver halide photographic photosensitive material
US5766834 *Sep 11, 1996Jun 16, 1998Eastman Kodak CompanyPhotographic element containing ultraviolet absorbing polymer
US5770353 *Jun 28, 1996Jun 23, 1998Eastman Kodak CompanyPhotographic element having improved ferrotyping resistance and surface appearance
US5856078 *Mar 12, 1997Jan 5, 1999Eastman Kodak CompanyAntihalation undercoat layer with improved adhesion and reduced finishing dirt
US5858633 *May 16, 1997Jan 12, 1999Eastman Kodak CompanyPhotographic elements containing 3-alkyl group substituted 2-hydroxyphenylbenzotriazole UV absorbing polymers
US5914223 *Mar 12, 1997Jun 22, 1999Eastman Kodak CompanyPhotographic element with outer layer having improved physical performance
US5919850 *Mar 12, 1997Jul 6, 1999Eastman Kodak CompanyUV absorbing polymer particle for use in imaging elements
US5948605 *Aug 16, 1996Sep 7, 1999Eastman Kodak CompanyUltraviolet ray absorbing polymer latex compositions, method of making same, and imaging elements employing such particles
US6030699 *Feb 22, 1999Feb 29, 2000Eastman Kodak CompanyUV absorbing polymer particle for use in imaging elements
US6143484 *May 6, 1999Nov 7, 2000Eastman Kodak CompanyMethod for stabilizing photographic dispersions in melts containing fine grain silver halide
US9329281Feb 19, 2014May 3, 2016Konica Minolta, Inc.Deposition substrate and scintillator panel
US9739895Apr 1, 2016Aug 22, 2017Konica Minolta, Inc.Deposition substrate and scintillator panel
US20040228986 *Mar 23, 2004Nov 18, 2004Tetsuto MiyanishiInterior ornament and indicator panel for vehicle
US20080263994 *Mar 4, 2005Oct 30, 2008Don KainMethod and apparatus for protecting a substrate
EP0147854A2Dec 27, 1984Jul 10, 1985Fuji Photo Film Co., Ltd.Silver halide photographic light-sensitive materials
EP0204175A1May 9, 1986Dec 10, 1986Fuji Photo Film Co., Ltd.Silver halide color photographic materials
EP0209118A2Jul 15, 1986Jan 21, 1987Konica CorporationSilver halide photographic material
EP0698817A1Aug 14, 1995Feb 28, 1996AGFA-GEVAERT naamloze vennootschapAssortment of silver halide photographic industrial X-ray films and method of processing said assortment
EP0772088A1Mar 4, 1992May 7, 1997Fuji Photo Film Co., Ltd.Heat-developable diffusion transfer color photographic material
EP0800113A2Apr 1, 1997Oct 8, 1997Fuji Photo Film Co., Ltd.Silver halide color photographic light-sensitive material
EP1016537A2Dec 28, 1999Jul 5, 2000Fuji Photo Film Co., Ltd.Method and apparatus for forming image with plural coating liquids
Classifications
U.S. Classification430/512, 546/269.7
International ClassificationF16G11/00, F16G11/10, G03C1/815
Cooperative ClassificationF16G11/10, G03C1/8155
European ClassificationF16G11/10, G03C1/815C