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Publication numberUS3449123 A
Publication typeGrant
Publication dateJun 10, 1969
Filing dateSep 3, 1965
Priority dateSep 8, 1964
Also published asDE1268493B
Publication numberUS 3449123 A, US 3449123A, US-A-3449123, US3449123 A, US3449123A
InventorsHideo Kondo, Nobuo Tsuji, Fumihiko Nishio, Eiichi Mizuki
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Color turbidity agent in color photographic materials
US 3449123 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,449,123 COLOR TURBHDITY AGENT IN COLOR PHOTOGRAPHI'C MATERIALS Hideo Kondo, Nobuo Tsuji, Fumihiko Nishio, and Eiichi Mizuki, Kanagawa-ken, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa-ken, Japan, a corporation of Japan No Drawing. Filed Sept. 3, 1965, Ser. No. 485,083 Claims priority, application Japan, Sept. 8, 1964, 39/51,200; Nov. 2, 1964, 39/61,917 Int. Cl. G03c 1/84 U.S. Cl. 96100 32 Claims ABSTRACT OF THE DISCLOSURE prevented.

The present invention relates to color photography and more particularly to an incorporated coupler type color photographic material containing a color turbidity preventing agent.

There has been known several types of color photographic materials containing in the photographic emulsion layers color couplers that form dye-images by coupling with the oxidation products of a N,N-dialkyl-pphenylenediamine type developing agents.

In one type of them, a coupler having an oil-soluble group is dissolved in a high boiling point oily solvent, and the solution is then dispersed in a gelatin solution containing a dispersing agent such as sodium alkylbenzene sulfonate, and then a mixture of thus prepared dispersion and a photographic emulsion is coated upon a suitable support.

In another type of them, an oil-soluble coupler in melt or in the form of solution in a low-boiling organic solvent is mixed with a photographic emulsion without using any water-immiscible high boiling point organic solvent followed by coating on a support.

In still another type of them, a water-soluble or an alkali-soluble group is introduced into a coupler having the long chain aliphatic hydrocarbon group and the coupler is incorporated in the form of alkaline solution in a photographic emulsion followed by coating on a suitable support.

In such a type of color photographic materials, there frequently occur such troubles that the color of the dyeimages become turbid, the purity of the color is reduced. Hereinafter, such a reduction of the color purity of color saturation is called color turbidity. It is because of the fact that the process of removing developed sliver by an oxidation bleaching bath after color development is often incompletely carried out and a part of the developed silver remains unoxidized. The spectrally broad light absorption band of the silver thus appears over the sharp light absorption band of the dye-image.

The inventors have found that by incorporating in a color photographic element particularly in a color photographic emulsion containing an oil-soluble coupler and a high boiling point oily solvent a polymer of vinylmethylimidazol having the following structure Patented June 10, 1969 N NCH3 HG: H

or 1-vinyl-2-methylimidazol having the structure In this case, the binding agent for the color photographic emulsion may be a suitably protective colloid, such as, gelatin, polyvinyl alcohol, a derivative thereof, polyacrylamide, a derivative thereof, a cellulose derivative, casein, and an alginate, but gelatin is most preferable.

The polymer used in this invention is a 2-vinyl-lmethylimidazol polymer of a polymer of l-vinyl-2- methylimidazol, or a copolymer containing the abovementioned vinyl-methylimidazol. The monomer to be copolymerized with the vinylmethylimidazol in this invention may be vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative thereof, methacrylamide, a derivative thereof, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid, vinyl pyrrolidone and the like. As the vinyl ester, there are vinyl acetate, vinyl propionate, vinyl butyrate and the like. As the acrylic ester, there are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. As the acrylamide derivative may be N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylarnide, N,N-diethylacrylamide, acryloil morpholine and the like. The methacrylamide derivative may be N-methylmethacrylamide, N-ethylmethacrylamide, methacryloil morpholine and the like.

For example, in the case of copolymer of the vinyl methylimidazol and vinyl acetate, the copolymer gives the best effect when the monomer molecular ratio is 7:3 but the copolymer having other monomer molecular ratio may be effectively used in this invention if it contains the vinyl methylimidazol. The polymer and the copolymer of the vinyl methylimidazol in this invention may be used alone or a mixture thereof.

The polymer or the copolymer used in this invention may be soluble in an alkaline solution or miscible in water in colloid state but more preferably be soluble in organic solvents.

The effect of the above-mentioned polymer or copolymer is not substantially influenced by the polymerization degree and the polymer of any polymerization degree may be used in this invention if it is soluble in the abovementioned solvents, liquid having high boiling point (at least above 200 C.) or solid. However, the transparency of the highlight portion of picture is better as the polymerization degree is higher.

The organic solvent utilized for dissolving the polymer or the copolymer in a photographic emulsion may be alcohols, such as, methanol, ethanol, isopropanol, etc.; ether alcohols, such as, Cellosolve, carbithols, etc.; esters, such as, ethyl acetate, butyl acetate, etc.; ethers, such as, ethylether, dioxane, tetrahydrofuran, etc.; ketones, such as, acetone, methylethyl ketone, etc.; amides, such as, lactams, dialkyl carbamides, etc.; and the like.

The mixing ratio of the polymer in a photographic emulsion is varied by the kind and amount of the coupler in the emulsion. In general, the optimum amount of the polymer is in the order of by weight based on the weight of gelatin present in the emulsion but the content may of course be larger than the value. However, since the coupling efficiency to dye-forming development and the physical properties of the film are lowered if the amount of the polymer is higher than 25%, a suitable mixing amount is generally about 5 to about 12%.

The invention may be applied effectively to any couplers used in color photographic elements but particularly good results are obtained when it is used with the following oil-soluble couplers.

Coupler 1.4-benzoylacetamido-N-butyl-N-octylbenzamide /(C 1103011; Q-o o omooNH-o ON\ (C H2)7CH3 Coupler 2.1-hydroxy-4-chloro-N-dodecyl-2-naphthamide Coupler 3 .1- (2,4,6-trichlorophenyl) -3- 3- (N-butyltetradecanamido -propanamido )pyrazoline-S-on The color turbidity preventing polymer or copolymer in this invention may be added at dispersing the coupler, at mixing the dispersion in a photographic 611111181011, or at coating the emulsion on a support, but the addition at dispersing the coupler is most preferable. Moreover, in this invention, the color turbidity preventing polymer or copolymer may be added in at least one of subsidiary layers of the color photographic element, such as, an antihalation layer, an insulating layer, a filter layer, a protective layer, and the like as the case may be, whereby the color turbidity of the adjacent emulsion layer can be prevented. In this case, the polymer or the copolymer gives remarkable effect when added in an amount more than 5% by weight and may be added into the subsidiary layers in an amount up to about 75% by weight of the gelatin without giving any bad influences on the physical properties of film and coupling efficiency.

The invention will further be explained more in detail by the following examples.

Example 1 Into a mixture of 1.2 ml. of d-ibutyl phthalate and 3.0 ml. of ethyl acetate was dissolved 4.0 g. of the abovementioned Coupler 1 by heating and the solution was added into ml. of a 10% aqueous gelatin solution containing 0.8 g. of a copolymer of 2-vinyl-1-methylimi'dazol and acrylamide (monomer ratio 7:3 and 2.0 ml. of a 10% aqueous solution of sodium alkylbenzene sulfonate and the mixture was homogenized with a high speed for 3 minutes at 4050 C. by means of a homo blender five times with intervals of 1 minute each to 4 prepare a dispersion of the coupler, the polymer and gelatin.

Thus prepared dispersion was added in a gelatino silver halide emulsion containing 4.5 g. of silver bromide and 7.5 g. of gelatin. After coating the emulsion on a film base, the emulsion layer was exposed and subjected to color treatments, such as, color development, water washing, potassium ferricyanide-bromide bleaching treatment, etc. Since a yellow coupler was used in this example, the degree of the turbidity of dye-image was determined by measuring the optical density with red filter. The results are shown in the following table.

TABLE 1 2-vinyl-l-methylimidazol-acrylamide copolymer, monomer ratio 7:3

Red optical density Not contained 0.79 Contained 0.38

The optical density 'value shows that by incorporating the copolymer of 2-vinyl-1-methylimidazole and acrylamide in the color photographic emulsion layer, the turbidity (the value of optical density in the wavelength region of no dye absorption) is reduced.

Example 2 Example 3 The same procedure as in Example 1 was repeated using a 2-vinyl-l-methylimidazol-acrylic acid copolymer (monomer ratio 7:3) instead of the copolymer in Example 1. The turbidity value was 0.28 in red optical density value.

Example 4 The same procedure as in Example 1 was repeated using a 2-vinyl-l rnethylimidazol-vinyl acetate copolymer (monomer ratio 7:3). The turbidity value was 0.29 in red optical value.

Example 5 The same procedure as in Example 1 was repeated using a 2-vinyl-l-methylimidazol-vinyl pyrrolidone copolymer (monomer ratio 7 :3). The turbidity value was 0.34 in red optical value.

Example 6 A color photographic element was prepared as in Example 1 using 2.40 g. of Coupler 2 instead of the coupler in Example 1. The photographic element was exposed and subjected to color treatments, such as color development, water-washing and potassium ferricyanide-bromide bleaching. In the case of using a cyan coupler as in this example, the cyan turbidity can be determined by meas uring the blue optical density value. The results are shown in the following table.

TABLE 2 Z-vinyl-1-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 2 (cyan): Blue optical density Not contained 0.91 Contained 0.51

Example 7 A color photographic element was prepared as in Example 1 using 4.30 g. of Coupler 3 instead of the coupler in Example 1. The element was exposed and subjected to color treatments, such as color development, waterwashing, and potassium ferricyanide-bromide bleaching. 1n the case of using a magenta coupler as in this example, the magenta turbidity value can be determined by measuring the red optical density value. The results are shown in the following table.

TABLE 3 2-vinyl-1-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 3 (magenta): Red optical density Not contained 0.63 Contained 0.39

Example 8 2-vinyl-1-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 2 (cyan): Blue optical density Not contained 0.91 Contained 0.68

Example 9 The same procedure as in Example 1 was repeated using a 1-vinyl-2-methylimidazol-acrylamide copolymer (monomer ratio 7 :3). The turbidity value was 0.35 in red optical density value.

Example 10 A 1-vinyl-2-methylimidazol polymer was used instead of the copolymer in Example 1. The turbidity value was 0.25 in red optical density value.

Example 11 A 1 vinyl 2 methylimidazol-acrylic acid copolymer (monomer ratio 7 :3) was used instead of the copolymer in Example 1. The turbidity value was 0.31 in red optical density value.

Example 12 A 1-vinyl-2-methylimidazol-vinyl acetate copolymer (monomer ratio 7:3) was used instead of the copolymer in Example 1. The turbidity value was 0.28 in red optical density value.

Example 13 A 1-vinyl-2-methylimidazol-vinyl pyrrolidone copolymer (monomer ratio 7:3) was used instead of the copolymer in Example 1. The turbidity value was 0.37 in red optical density value.

Example 14 A color photographic element was prepared as in Example 1 using 2.40 g. of Coupler 2 instead of the coupler in Example 1. The element was exposed and subjected to color treatments, such as, color development, waterwashing, and potassium tEerricyanide-bromide bleaching. In the case of using cyan coupler as in this example, the cyan turbidity can be determined by measuring the blue optical density value. The results are shown in the following table.

TABLE 5 1-vinyl-2-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 2 (cyan): Blue optical density Not contained 0.91 Contained 0.41

Example 15 A color photographic element was prepared by the same manner as in Example 1 using 4.30 g. of Coupler 3 instead of the coupler in Example -1. The photographic element was exposed and subjected to color development, water washing, and potassium terricyanide bromide bleaching. In the case of using a magenta coupler as in this example, the magenta turbidity was determined by measuring the red optical density value. The results are shown in the following table.

TABLE 6 1-vinyl-2-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 3 (magenta): Red optical density Not contained 0.63 Contained 0.43

Example 16 A coating solution of 0.80 g. of a 1-vinyl-2-methylimidazol-acrylamide copolymer (monomer ratio 7:3) in g. of an aqueous 3% (by weight) gelatin solution was coated as an intermediate layer upon a red-sensitive silver halide layer containing the cyan coupler. T hus prepared photographic element was exposed and subjected to color treatments, such as, color development, water-washing, and potassium Iferricyanide-bromide bleaching. The turbidity value of the cyan coupler is shown in the following table in blue optical density value.

TABLE 7 1-vinyl-2-methylimidazol-acrylamide copolymer (monomer ratio 7:3)

Coupler 2 (cyan) Blue optical density Not contained 0.91 Contained 0.63

What is claimed is:

1. A color photographic gelatino silver halide material comprising a support and at least one photographic gelatino silver halide emulsion layer containing a color coupler, and at least one of said layers containing a polymer material selected from the group consisting of a polymer of the vinyl-methylimidazol shown by the general formula.

(wherein R and R each represents a member selected from the group consisting of CH =CH and CH said R and R being different from each other and a copolymer of said vinylmethylimidazol and a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, methacrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid, and vinyl pyrrolidone.

2. The color photographic silver halide material as claimed in claim 1, wherein said polymer material is selected from a polymer of 2-vinyl-1-methylimidazol shown by the formula HC=OH and a copolymer thereof with a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid and vinyl pyrrolidone.

3. The color photographic silver halide material as claimed in claim 1, wherein said polymer material is selected from a polymer of 1-vinyl-2-methylimidazol shown by the formula and a copolymer thereof with a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, methacrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid and vinyl pyrrolidone.

4. The color photographic silver halide material as claimed in claim 1 wherein said polymer material is in said photographic emulsion layer and the amount of said polymer material in the emulsion layer is to 25 percent by weight based on the amount of gelatin in the emulsion layer.

5. The color photographic silver halide material as claimed in claim 1 wherein said coupler is 4-benzoylacetamido-N-octylbenzamide.

6. The color photographic silver halide material as claimed in claim 1 wherein said coupler is 1-hydroxy-4- chloro-N-dodecyl-Z-naphthamide.

7. The color photographic silver halide material as claimed in claim 1 wherein said coupler is 1-(2,4,6- trichlorophenyl)-3-(3 (N butyltetradecanamido) propanamido) -pyrozoline-5-on.

8. A color photographic gelatino silver halide material comprising a support, at least one photographic gelatino silver halide emulsion layer containing an oil soluble color coupler, an antihalation layer, an intermediate layer, a filter layer, and a protective layer, at least one of said layers containing a polymer material selected from the group consisting of a polymer of the vinylmethylimidazol shown by the general formula l HC=CH wherein R and R each represents a member selected from the group consisting of CH ==CH and CH said R and R being different from each other and a copolymer of said vinylmethylimidazol and a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, methacrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid, and vinyl pyrrolidone.

9. The color photographic silver halide material according to claim 8, wherein the coupler forms dye-images by coupling with the oxidation product of a N, N-dialkylp-phenylene-diamine type developing agent.

10. The color photographic silver halide material as claimed in claim 8, wherein said polymer material is selected from a polymer of 2-vinyl-1-methylimidazol shown by the formula and a copolymer thereof with a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, methacrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid and vinyl pyrrolidone.

11. The color photographic silver halide material as claimed in claim 8, wherein said polymer material is selected from a polymer of 1-vinyl-2-methylimidazol shown by the fomnula N NCH=CHI HC CH and a copolymer thereof with a monomer selected from the group consisting of vinyl ester, acrylic acid ester, methacrylic acid ester, acrylamide, a derivative of acrylamide, methacrylamide, a derivative of methacrylamide, acrylic acid, methacrylic acid, styrene, styrene sulfonic acid and vinyl pyrrolidone.

12. The color photographic silver halide material as claimed in claim 8 wherein said polymer material is in said photographic emulsion layer and the amount of said polymer material in the emulsion layer is 5 to 25 percent by weight based on the amount of gelatin in the emulsion layer.

13. The color photographic silver halide material as claimed in claim 8 wherein said coupler is 4benzoylacetamido-N-octylbenzamide.

14. The color photographic silver halide material as claimed in claim 8 wherein said coupler is l-hydroxy-4- chloro-N-dodecyl-Z-naphthamide.

15. The color photographic silver halide material as claimed in claim 8 wherein said coupler is 1-(2,4,6- trichlorophenyl) 3 (3 N butyltetradecanamido)- propanamido)-pyrozoline-5-on.

16. The color photographic silver halide material as claimed in claim 8 wherein at least one of said layers contains 5 to 75 percent by weight based on the amount of gelatin of the polymer material.

17. The color photographic silver halide material as claimed in claim 9 wherein said copolymer is a 2-vinyl-1- methylimidazol-acrylamide copolymer.

18. The color photographic silver halide material as claimed in claim 9 wherein said copolymer is a 2-vinyl-lmethylimidazol-acrylic acid copolymer.

19. The color photographic silver halide material as claimed in claim 9 wherein said copolymer is a 2-vinyll-methylimidazol-vinyl acetate copolymer.

20. The color photographic silver halide material as claimed in claim 9 wherein said copolymer is a 2-vinyl-1- methyli'midazolwinyl pyrrolidone copolymer.

21. The color photographic silver halide material as claimed in claim 10 wherein said copolymer is a 2-vinyll-methylimidazol-acrylamide copolymer.

22. The color photographic silver halide material as claimed in claim 10 wherein said copolymer is a 2-vinyll-methylimidazol-acrylic acid copolymer.

23. The color photographic silver halide material as claimed in claim 10 wherein said copolymer is a 2-vinyll-methylimidazol-vinyl acetate copolymer.

24. The color photographic silver halide material as claimed in claim 11 wherein said copolymer is a 2-vinyll-methylimidazol-vinyl pyrrolidone copolymer.

25. The color photographic silver halide material as claimed in claim 3 wherein said copolymer is a l-vinyl- 2-methylimidazol-acrylamide copolymer.

26. The color photographic silver halide material as claimed in claim 3 wherein said copolymer is a l-vinyl- Z-methylimidazol-acrylic acid copolymer.

27. The color photographic silver halide material as claimed in claim 3 wherein said copolymer is a l-vinyl- Z-methylimidazol-vinyl acetate copolymer.

28. The color photographic silver halide material as claimed in claim 3 wherein said copolymer is a l-vinyl- 2-methylimidazol-vinyl pyrrolidone copolymer.

29. The color photographic silver halide material as claimed in claim 11 wherein said copolymer is a l-vinyl- Z-methylimidazol-acrylamide copolymer.

30. The color photographic silver halide material as claimed in claim 11 wherein said copolymer is a l-vinyl- Z-methylimidazol-acrylic acid copolymer.

References Cited UNITED STATES PATENTS 4/1964 Schwerin 96-114 NORMAN G. TORCHIN, Primary Examiner. MARY F. KELLEY, Assistant Examiner.

US. Cl. X.R.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3130050 *Jan 18, 1960Apr 21, 1964Gen Aniline & Film CorpOil-dispersed dyes in photopolym-erization systems
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3907572 *Jan 25, 1974Sep 23, 1975Mitsubishi Paper Mills LtdColor photographic photosensitive emulsion and color photographic material
US3912513 *Jan 11, 1974Oct 14, 1975Agfa Gevaert NvPolymeric competing couplers and their use in photographic silver halide colour materials
US4766052 *Aug 17, 1987Aug 23, 1988Fuji Photo Film Co., Ltd.Photographic element with polymeric imidazole dye mordant
US4957857 *Dec 23, 1988Sep 18, 1990Eastman Kodak CompanyStabilization of precipitated dispersions of hydrophobic couplers
US5015564 *Jun 1, 1990May 14, 1991Eastman Kodak CompanyStabilizatin of precipitated dispersions of hydrophobic couplers, surfactants and polymers
US5087554 *Jun 27, 1990Feb 11, 1992Eastman Kodak CompanyStabilization of precipitated dispersions of hydrophobic couplers
US5256527 *Sep 9, 1991Oct 26, 1993Eastman Kodak CompanyStabilization of precipitated dispersions of hydrophobic couplers
Classifications
U.S. Classification430/545, 430/941, 430/630, 430/510
International ClassificationG03C7/396, G03C1/053, G03C7/30, G03C7/413
Cooperative ClassificationG03C7/3005, G03C1/053, G03C7/413, Y10S430/142, G03C7/396
European ClassificationG03C7/30C1, G03C1/053, G03C7/413, G03C7/396