US3847613A - Silver halide photosensitive materials for color photography - Google Patents

Silver halide photosensitive materials for color photography Download PDF

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US3847613A
US3847613A US32533873A US3847613A US 3847613 A US3847613 A US 3847613A US 32533873 A US32533873 A US 32533873A US 3847613 A US3847613 A US 3847613A
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group
emulsion layer
sensitive emulsion
silver halide
ch2
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N Fujimori
K Sakazume
S Ito
E Sakamoto
K Mine
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Konica Corp
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Konica Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16Methine and polymethine dyes with an odd number of CH groups with one CH group

Abstract

Wherein Y1 and Y2 each stand for a non-metallic atomic group necessary for forming a nitrogen-containing heterocyclic ring nucleus selected from the group consisting of pyrroline, thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline, which heterocyclic ring nucleus may be substituted by a halogen atom, a lower alkyl group, a lower alkoxy group, or an aryl group, which group may be substituted by a halogen atom, a lower alkyl group or a lower alkoxy group; R1 stands for a lower alkyl group, a hydroxyalkyl group, or a sulfoalkyl group; R2 is a hydrogen atom or a lower alkyl group; A designates an alkylene group or a group -(CH2)2 -O -(CH2)2 -or, -(CH2)2-O -CH2CH(OH) CH2-; and n1 and n2 are each 0 or 1.

A silver halide photosensitive material for color photography providing excellent color reproducibility is disclosed which comprises a support and at least three emulsion layers supported thereon; said layers being a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer; the blue-sensitive emulsion layer containing a sensitizing dye represented by the following formula:

Description

United States Patent [191 S akazume et al.

[ 1 Nov. 12, 1974 1 SILVER HALIDE PHOTOSENSITIVE MATERIALS FOR COLOR PHOTOGRAPHY Konishiroku Photo Industry Co. Ltd., Tokyo, Japan Filed: Jan. 22, 1973 Appl. No.: 325,338

[73] v Assignee:

[30] Foreign Application Priority Data References Cited UNITED STATES PATENTS 8/1939 Brooker H 96/140 x 2/1941 Brooker et a1 96/132 X l/l960 Henrilarive et al. 96/140 X 9/1964 Henrilarive et al. 96/1'32 X Primary ExaminerDavid Klein Assistant Examiner-Alfonso T. Suvo Pico Attorney, Agent, or FirmBierman & Bierman [57] ABSTRACT A silver halide photosensitive material for color photography providing excellent color reproducibility is disclosed which comprises a support and at least three emulsion layers supported thereon; said layers being a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer; the blue-sensitive emulsion layer containing a sensitizing dye represented by the following formula:

Wherein Y and Y each stand for a non-metallic atomic group necessary for forming a nitrogencontaining heterocyclic ring nucleus selected from the group consisting of pyrroline, thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline, which heterocyclic ring nucleus may be substituted by a halogen atom, a lower alkyl group, a lower alkoxy group, or an aryl group, which group may be substituted by a halogen atom, a lower alkyl group or alower alkoxy group; R stands for a lower alkyl group, a hydroxyalkyl group, or a sulfoalkyl group; R is a hydrogen atom or a lower alkyl group; A 929511939 anralkylqp gro p 3 g p, (CH )2 O (CH2)2 0r, (CH -O Cl-l CH(OH) CH and n and n are each 0 or 1.

5 Claims, 2 Drawing Figures t 2 E: m a"' l 2 w I (D WAVE LENGTH(m/.L)

t 2 b (I) Z LIJ U) I I l I n WAVE LENGTH (my) PATENTED NOV 12 B74 FIG.I

I WAVE LENGTH (my) 500 WAVE LENGTH (my) SILVER HALIDE PHOTOSENSI'I IVE, MATERIALS VFOR COLOR PHOTOGRAPHY This invention relates to a silver halide photosensitive material for color photography. More particularly, it 5 emulsion layer:

sitive material for color photography which includes a blue sensitive emulsion layer sensitized by a spectral sensitizer.

In silver halide photosensitive materials for color photography,.chemical sensitization using sulfur or spectral sensitivity in the blue sensitive emulsion layer especially toward the longer wavelengths. Attempts have been made to increase the sensitivity of the bluesensitive emulsion layer in the range of the longer wavelengthsby the use of a spectral sensitizer.

However, most dyes heretofore used for this purpose are too effective and expand the photosensitive region of the blue sensitive emulsion layer excessively toward the longer wavelength region. This forms an image. of an undesirable yellow color and degrades the color reproducibility in the green image. Also, it reduces the sensitivity inherent in the silver halide and leaves color stains on the photosensitive material after development. Because of these defects, such dyes are not completely satisfactory as spectral sensitizers for the blue sensitive emulsion layer. Moreover, when photosensitive materials prepared with such dyes are stored under high temperature and humidity conditions, the sensitivity of the blue sensitive emulsion layer is drastically lowered, resulting in formation of fog or color stain. With the recent demand for acceleration of the processing of photosensitive materials, high temperatures are necessary. When photosensitive materials comprising such sensitizing dyes are developed at such high temperatures, the developing rates in the red sensitive emulsion layer and, the green sensitive emulsion layer differ from that of the blue sensitive emulsion layer. As a result, good balance of the photographic characteristics of these three layers is not obtained and the color reproducibility is greatly impaired. Accordingly, sensitizing dyes suitable for the blue sensitive emulsion layer, without such defects, has been long sought by those skilled in the art.

It is, therefore, a primary object of this invention to provide a coupler-containing, silver halide, photosensitive material for color photography having excellent color reporducibility, which comprises a blue sensitive emulsion layer sensitized by sensitizing dyes free of the afore mentioned defects.

This object can be attained by using a silver halide photosensitive material comprising a support and at I! V Y 'I 1 $2 I! 2 6 11 8 tca=cm c=c-c t=ca-cm ;-;=N,-A-'so relates toacoupler-containing, silver halide, photosen- Wherein Y and Y each stand for a non-metallic atomic group necessary for forming a nitrogen containing heterocylic ring nucleus selected from the group consisting of pyrroline. thiazoline. thiazole. benzothiaz ole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole. naphthoxazole, imidazole, benzimidazole, pyridine and quinoline; which nucleus may be substituted by a halogen atom, a lower alkyl group, a lower alkoxy group or an aryl group; which group may in turn be substituted by halogen, lower alkyl or lower alkoxy; R stands for lower alkyl, hydroxy alkyl, carboxyalkyl or sulfoalkyl; R is hydrogen or lower alkyl; A designates alkylene.-(CH- 2 O(Cl-l or (CH OCH CH(OH)CH and n and n are each 0 or 1.

Typical examples of compounds expressed by the above general formula and useful in this invention are listed below. However. the list is exemplary only and is not intended to limit the invention.

Maximum absorption in methanol a) S I CH \N CHa (HakSO (I EH: N (+)N baton eaaasoa- CH- I G l (CH?)3SO3H (Cfimso w (4) Se Se H3 Q as HaC -OC] N +)N CHa) SOZH (liJHz) S 0 (5) S Se\ 131 l \ZC I, .3 l l c: N WN l 4 112000" ll elzis ():l

3 4 Continued Continued Maximum Maximum absorption 7 absorption in methanol in methanol (mp) i S 's' 42s 15 "5 s (6) 5 =CH =oH Cl N ("UN III (UN 32m I (33201120 grriorr sow 7 l0 (CH2)2(|3HSO3H oHnionso w or H 7 s Se 448 3 (l6) C113 C113 430 =CH Cl C N (MN i :OH- (CH2)aSO31-I oimisoaw 17 11: H2 s 400 =CH- i H 1 on Y M CH; oHa soi CH3 (+)N l (CH2)3SO3( OH \N CH3 30 (18) H H? 422 Wilma? ,7 i H LCH J N (10) S 384 (1 H va) HP camisole) =c1 H 0 o 3110 \N N/ (IJZHS (&H2)20(CH2)3SO3( =CII n) on, 410 \N 1 40 411 m onaisow Q =CH The co nipound s of the generalformula useful H N in this invention can readily be synthesized by methods 1 5 disclosed in, for instance, specification of British Pat.

3 bows amusem- .NQ- 49.

The compounds of the present invention are preferafi l? f ff bly added to the emulsions in the form of solutions in (19) s s 427 a watermiscible organic solvent such as methanol or u ethanol. The addition of such compounds may be effected at any desired point during the preparation of the emulsions. In general, however, it is preferable that N N they be added just after the chemical ripening or chemr y n onmogmoncmso w ical sensitization. The compounds are incorporated in H an amount of 0.01 to 0.5 g per mole of silver halide, alwe though the preferred amount can vary depending on 382 the kind of additiye and silver halide emulsion.

1 I I 02m (ormaso w (14) st So 430 =CH N +)N Thecouplers to be incorporated in the silver halide photosensitive materials for color photography are not particularly critical in this invention, and couplers customarily used in this field can be used effectively. For instance, the blue sensitive layer may contain a compound which can react with an oxide of a color developer containing a primary amino group to form a ycllow dye. The amount of such coupler to be added in generally 1.0 to 200g per mole of the silver halide. The coupler is preferably incorporated into the emulsion as an aqueous alkalisolution or as a solution in a high or low boiling point organic solvent.

It is also possible to incorporate other photographic additives such as stabilizers, film-hardening agents, pl-ladjusting agents, viscosityincreasing agents, coating assistants and color stain preventive agents in thephotosensitive material. Synthetic and natural high molecule compounds such as gelatin, casein and polyvinyl alcohol can be used singly or in combination as a binder.

The silver halide may, for example, be silver chloride,

, silver bromide, silver iodide-bromide and silver chloride-iodide-bromide. Various materials such aspaper,

I cellulose acetate film, polyester film, polycarbonate and polyolefineoated paper may be used as the support. The silver halide photosensitive material according to this invention can achieve a good balance in photographic characteristics between the red, green and blue sensitive layers even in high-temperature, high-speed development. It is also one of the advantages of this invention that the silver halide photographic material is freer from spot-like fog than the photographic material of the prior art. Spot-like fog often arises during development according to prior art'and is believed to result from a small quantity of fine metal stuck to the surface of the photosensitive material during its preparation,

processing or during actual photographing.

This discovery is further illustrated in more detail by the following Examples, which illustrate but do not limit the invention.

Example 1 Composition of Coupler Dispersion Coupler 100 g Dibutyl phthalate lOO ml Ethyl Acetate 300 ml 5% Aqueous solution of Alkano'l B (manufactured by Du Pont) 150 ml 6% Aqueous solution of gelatin 500 ml Then, a stabilizer, a film-hardening agent, a coating assistant and a pH-adjusting agent were-added to the emulsion to form a red sensitive emulsion.

Similarly, a green sensitive emulsion was prepared by using a sensitizing dye, anhydro-5,5-diphenyl-3,3'- disulfopropyl-9-ethyl-oxacarbocyanine hydroxide in an amount of 0.l5g per mole of the silver halide and, as a coupler, l-( 2,4,6-trichloro-phenyl -[3-(2,4-di-tertiary-amylphenoxyacetamide)benzamid]-5-pyrazolone in an amount of 60g per mole of the silver halide.

A color negative emulsion of silver bromideiodide containing 4.5 mole percent of silver iodide was chemically ripened and divided into seven portions. From these seven portions of the emulsion, seven kinds of blue sensitive emulsions were prepared by adding compounds (7), (9) or 14) of this invention individually in g 7 an amount of 0.00g, 0. 10g or 0.l5g per mole ofthfe silamt-halide; Aft r.-thq..ts. tins mtXt ts w e. sa jfir ciantly agitated to stabilize the absorption of the sensitizing dyes, g per mole of silver halide of 4-dodecylbenzoyl-Z'-methoxyacetoanilide was incorporated as a yellow coupler into each mixture in the form of a cow pler dispersion. The dispersion was prepared in the same manner as the above described red and green sensitizing emulsions. Then a stabilizer, a film-hardening agent, a coating assistant and a pH-adjusting agent were incorporated into each of the resulting compositions.

For each of the blue sensitive emulsions, a photographic film was prepared by coating on a cellulose triacetate film base. An anti halation layer, a red sensitive emulsion layer, a gelatin film layer, a green sensitive layer, a colloidal silver-containing yellow filter layer, a blue sensitive and a gelatin protective layer were successively coated on the base in that order.

These seven samples were exposed to artificial daylight of l60 luxes (5,400K) by employing a sensitometer (model KS-l manufactured by Konishiroku Photo Industry Co., Ltd. and subjected to the color development treatment according to the following procedures:'

Color Development Steps and Recipes (l) Color Development (24C.. [2 minutes) Benzyl alcohol Anhydrous sodium sultite N-Ethyl-N-B-methanesulfonamide ethyl-3 methyl-4-aminoaniline sulfate Sodium carbonate (monohydrate) Potassium bromide Water to make 7 l lite The p" was adjusted to 10.8 by addition of sodium hydroxide.

First Fixation (24C., 5 minutes) I50 g of sodium thiosulfate was added to enough water to make 1 liter of solution Water Washing (24C.. 5 minutes) Bleaching (24C., 6 minutes) Formula:

Potassium ferricyanide Potassium bromide Water to make Water Washing (24C.. 5 minutes) Second Fixation (24C.. 5 minutes).

g 50 g 1 liter (5) (6) the same recipe as that of the first fixation (7) (3) Water Washing (24C.. 10 minutes) Drying With respect to each of the resulting color negative images, the relative blue light sensitivity of the blue sensitive emulsion layer and the degree of the residual coloration were measured and the results are shown in Table l. The relative sensitivity is expressed as a relative value based on the blue light sensitivity (100) of the sample'( 1) containing no sensitizing dyes, and the degree of the residual coloration is expressed as a value of the complementary color concentration at the nonimage area.

Table l readily be-understood that the samples containing the.

Belgian Pat. No. 738,921 )1 compounds of this invention exhibit not only a low degr'ee of the residual coloration but also a high blue light sensitivity and are thus particularly suitable as sensitizing dyes for blue sensitive emulsion.

Example 2 A color reversable emulsion of silver iodidebromide containing 5 mole of silver iodide was chemically ripened and 0.15g per mole of silver halide of anhydro 5,- 5-disulfopropyl-9-ethyl-thiacarbocyane hydroxide was added as a sensitizing dye to the emulsion in the form of a methanol solution. Then 50g per mole of 4-chlorol-hydroxy-2-n-octylnaphthamide was added as a cyan coupler in the form of a dispersion prepared in the same manner as in Example 1, the resulting was well mixed and dispersed. A stabilizer, a film-hardening agent, a coating assistant and a pl-l-adjusting agent,

According to the same procedures as set forth above with respect to the preparation of the red sensitive emulsion, a green sensitive emulsion was prepared by employing, as a sensitizing dye, anhydro-5,5'-diphenyldisulfopropyl-9-ethyl-oxacarbocyanine hydroxide in an amount of 0.15g per mole of the silver halide and, as a magenta coupler, l-(3-carboxyphenyl)-3-(4- stearoylaminophenyl)-5-pyrazolone in an amount of 6X52, 9 sf es lterba jsie \N f S I Comparative dye B (disclosed in the specification of Pat. No. 3,480,434):

With use of the so prepared red, green, and 9 blue sensitive emulsions, layer structures were formed on cellulose triacetate film bases having an antihalation layer, in the same manner as in Example 1, thereby obtain 9 silver halide color reversal photosensitive materials differing only in the blue sensitive layer. These photosensitive materials were used as test samples.

In the same manner as in Example 1, these samples exposed to light, and the high-temperature, high-speed reversal color development was carried out according to the following steps to obtain color positive images:

Reversal Color Development Steps and Recipes (I) FilmPrehardening (38C., 2 minutes and 30 seconds 5 ml I54 g 20 g 27 ml llitcr 50% Aqueous solution of sulfuric acid Sodium sulfate Sodium acetate 37% Aqueous solution of formalin Water to make Neutralization (38C. 30 seconds) (3) First Development (38C.. 2 minutes and 30 minutes) Sodium polyphosphate Sodium bisulfite Phcnidone Hydroquinone Sodium Carbonate (monohydrate) 1071 Aqueous solution of potassium thiocyanide Potassium bromide 0.] 7r Aqueous solution of potassium iodide Anhydrous sodium sulfite Water to make l liter (4) First Stopping Water Washing (38C.. l minute) Reversal Light Explosure Color Development (38C. 3 minutes and 40 seconds) Sodium polyphosphate 5 Benzyl alcohol 5 Anhydrous sodium sulfite 7 Sodium phoshate 35 Potassium bromide l 0.1% Aqueous solution of potassium iodide Sodium hydroxide 3 4-Amino-N-methyl'N-(B-methanesulfoamide-ethyl)-m-toluyl-B- phenyl-ethylamine hydrochloride Water to make 1 Second Stopping (38C.. 30 seconds) Water Washing (38C., I minute) (10) Bleaching (38C., 1 minute and 30 seconds) Potassium ferrieyanide I00 g Potassium bromide 50 g Water to make 1 Water Washing (38C., 20 seconds) Fixation (38C., 1 minute and 30 seconds) Sodium thiosulfate 150 g Water to make 1 (13) Water Washing (38C., 1 minute) l4) Drying With respect to each of the color positive images obtained, the relative sensitivities of the blue sensitive layers and the blue densities (D min) of the high light portions were determined. The results are shown in table 2. In the Table, the Immediate Test data were obsinsstwlisn l1ifhbl Prep Samples were tested The Test after Preservation data were obtained when the samples were tested after they had been maintained at high temperature (50C) and high humidity relative humidity 80 percent for 2 days. The relative sensitivity is expressed as a relative value based on the sensitivity in the Immediate Test" of the sample containing no sensitizing dye in the blue sensitive layer.

Table 2 Sample dye Added and Its Amount Immediate Test Test after Preservation compound (12) 0. l 2 0.07

With respect to each of samples subjected to the imjected to high-temperature, high-speed reversal color mediate test, the values of the maximum density (D max), the minimum density (D min) and gamma (r) of each of the'sensitive layers were determined to evaluate their photographic characteristics. The results development under the same conditions as described above.

In the samples containing no sensitizing dye in the blue sensitive layer (8) and containing the prior art forming an aqueous suspension of zinc. The sample was dipped for seconds in this suspension and dried. withoutsxpqsqfstql b hstrs dsam w s' shown in Table} were obtained. 25 comparablef dyes in theblue (9-12), 90 to 120 fog Table 3 Sample Added dye and Its Photographic Characteristics of Three Lavers Amount (g per mole of Blue Sensitive Green Sensitive Red Sensitive No. halide) Emulsion layer Emulsion Luyer Emulsion Layer Kind Amount Dmax Dmin r Dmax Dmin r Dmux Dmin r 8 0.06 1.90 3.3 0.05 2.10 3.4 0.03 2.12 9 comparative colorant (A) 0.10 3.2 0.07 1.85 3.3 0.05 2.10 3.4 0.0. 2.12 10 comparative colorant (A) 0.20 3.1 0.08 1.91 3.3 0.05 2.10 3.4 0.03 2.12

l l comparative colorant (B) 0.10 3.2 0.08 1.94 3.3 0.05 2.10 3.4 0.03 2.12 l 2 comparative colorant (B) 0.20 3.1 0.08 1.98 3.3 0.05 2.10 3.4 0.03 2.12 l 3 illustrated compound (4') 0.10 3.3 0.06 2.11 3.3 0.05 2.10 3.4 0.03 2.12 14 illustrated 7 compound (4) 0.20 3.4 0.07 2.10 3.3 0.05 2.10 3.4 0.03 2.l2 l 5 illustrated compound (12) 0.10 3.3 0.06 2.12 3.3 0.05 2.10 3.4 0.03 2 12 16 illustrated compound (12) 0.20 3.3 0.07 2.10 3.3 0.05 2.10 3.4 0.03 2.12

From the results shown in Tables 2 and 3, it will readspots were formed per 100 cm*. However, according to ily be understood that silver halide photosensitive mathe present invention (l3-l6), only 20 to of fog terials prepared with use of sensitizing dyes of this inspots were formed per 100cm? As is apparent from the vention are far superior to the silver halide photosensiforegoing results, the dyes of this invention control the tive materials with no sensitizing dye as well as those formation of fog spots resulting from the presence of usingcomparable prior art dyes. The blue light sensifine metalhc powder. tivity is much higher and the sensitivity reduction after storage under high temperature and high humidity con- Example V V dltcllons Ve.ry ia f y lsblowebr According to the procedures of Example 1, various a C ear Image 0 no C0 Ora can silver halide color negative photosensitive materials tamed. Moreover, even when high-temperature, highwe re prepared as follows. speed development 1s used a good balance is attained among the three emulsion layers and thereby excellent Y a1 6 co 9 P otosensmve color reproducibility is Obtained rial contammg no sensmzmg dye in the blue sens1t1ve In order to test formation of spot-like fog, immedilayer; h ate test samples (8) to 16) w r bj d to h f l. four s1lver hahde color negatwe photosensitive matel i t; rials containing 0.10 or 0.l5g per mole of silver halide 200mg of metallic zinc powder was added to SI of Of Q PP 0r Of this mventlon m the b water under a agitation and the resultant mixture was l il Q 951 filtered to remove the larger zinc particles. thereby four silver halide color positive photosensitive materials containing comparative dyes (C) or (D) in an amount of 0.10 or 0. l-5g per mole of silver halide in the blue sensitive layer.

These samples were exposed to light under the same conditions as in Example 1. and color negative images were obtained by color development treatment according to the same procedures as in Example 1 except that the treatment temperature 1 and treatment time were changed as indicated below.

Color Development Treatment samples they were maintained at a temperature of C.. and a relative humidity of percent for 2 days. They were then exposed tolight and subjected to the color development in the same manner as described above to obtain the color negative image.

With respect to each of the resulting color negative images, the blue light sensitivity of the blue sensitive layer and the residual coloration were determined and the results are shown in Table 4. 1n the Table, the 1mmediate Test data were obtained from the fresh samples and the Test after Preservation" data were obtained from samples which had been stored under the high temperature and high humidity conditions as de Table 4 scribed above. The relative sensitivity is a relative value based on the value (100) of the sensitivity in the 1mmediate Test of the sample containing no sensitizing dye in the blue sensitive layer, and the residual coloration is expressed in terms of the value of the complementary color concentration of the non-image area.

From the results shown in Table 4, it will easily be understood that silver halide photosensitive material prepared in accordance with this invention is far superior to silver halide photosensitive materials without any sensitizing dye as well as those materials using prior art comparable dyes. When the high-temperature development treatment is applied, a higher blue light sensitivity is attained, and, even afterstorage under high temperature and high humidity conditions, the reduction in sensitivity is extremely slight and a sufficient sensitivity is retained. Moreover, the degree of the residual coloration is low, resulting in a very clear image.

The spectrophotography was conducted on the same samples as described above to examine the spectral sensitivity curves of blue sensitive emulsion layers. The results are shown in FIGS. 1 and 2.

In FIG. 1, broken line (1) is the spectral sensitivity curve of the blue sensitive emulsion layer of sample (23) having compound (3) of this invention therein in an amount of 0.15g per mole of silver halide. Solid line (2) is the spectral sensitivity curve of the blue sensitive emulsion layer of sample 17) containing no sensitizing dye.

In FIG. 2, broken line (3) is the spectral sensitivity curve of sample (25) having compound (14) of this in- Sample dye Added and Its Amount (g per mole Immediate Test Test after Preservation No. of silver halide) Kind Amount Relative Residual Relative Residual Sensitivity Sensitivity Sensitivity Coloration l7 100 0.11 93 0.13 18 comparative colorant (C) 0.10 94 0.12 88 0.14 19 comparative colorant (C) 0.15 90 0.12 86 0.14 20 comparative colorant (D) 0.10 92 0.12 89 0.14 21 comparative colorant (D) 0.15 95 0.12 90 0.14 22 illustrated compound (3) 0.10 0.11 125 0.11 23 illustrated compound (3) 0.15 140 0.11 135 0.11 24 illustrated cp,pimd (14) 0.10 0.11 120 0.11 25 illustrated compound (14') 0.15 0.12 130 0.12

vention therein in an amount of 0.15g per mole of the layer, and a blue-sensitive emulsion layer: the bluesensitive emulsion layer containing a sensitizing dye represented by the following formula:

Wherein Y and Y each stand for a non-metallic atomic group necessary to form a nitrogen-containing heterocyclic ring nucleus selected from the group consisting of pyrroline, thiazoline, thiazole, benzothiazol, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxozole, imidazole, benzimidazole, pyridine, and quinoline, which nucleus 'maybe substituted by a halogen atom, a lower 14 alkyl group, a lower alkoxy group, or an aryl group, which group may in turn be substituted by halogen, lower alkyl or lower alkoxy; R stands for lower alkyl, hydroxyalkyl, or sulfoalkyl; R is hydrogenor lower alkyl, A designates alkylene,

2. A silver halide photosensitive material for color photography according to claim 1, wherein each of said layers contains a coupler.

3. A silver halide photosensitive material for color photography according to claim 1, wherein said heterocyclic ring nucleus in said general formula is selected from thiazole, benzothiazole, selenazole, and benzoselenazole.

4. A silver halide photographic material for color photography according to claim 1, wherein said bluesensitive emulsion layer contains a yellow coupler, said green-sensitive emulsion layer contains a magenta coupler, and said red-sensitive emulsion layer contains a cyan coupler.

5. A silver halide photosensitive material for color photography according to claim 4, wherein said heterocyclic nuclei in said sensitizing dye are each selected from thiazole, benzothiazole, selenazole, and benzoselenazole.

Claims (5)

1. A SILVER HALIDE PHOTOSENSITIVE MATERIAL FOR COLOR PHOTOGGRAPHY COMPRISING A SUPPORT AND AT LEAST THREE EMULSION LAYERS SUPPORTED THEREON, SAID LAYERS BEING A RED-SENSITIVE EMULSION LAYER, A GREEN-SENSITIVE EMULSION LAYER, AND BLUE-SENSITIVE EMULSION LAYER: THE BLUE-SENSITIVE EMULSION LAYER CONTAINONG A SENSITIZING DYE REPRESENTED BY THE FOLLOWING FORMULA: (-Y1-N(-R1)-(CH=CH)N1-)>C=C(-R2)-C<(-Y2-N(+)-A-SO3(-))= (CH-CH=)N2) WHEREIN Y1 AND Y2 EACH TAND FOR A NON-METALIC ATOMIC GROUP NECESSARY TO FORM A NITROGEN-CONTAINING HETEROCYCLIC RING NUCLEUS SELECTED FROM THE GROUP CONSISTING OF PYRROLINE, THIAZOLINE, THIAZOLE, BENZOTHIAZOL NAPHTHOTHIAZOLE, SELENAZOLE, BENXOSELENAXOLE, NAPHTHOSELENAZOLE, OXAZOLE, BENZOXAZOLE, NAPHTHOXOZOLE, IMIDZOLE, BENZIMIDAZOLE, PYRIDINE, AND QUINOLINE, WHICH NUCLEUS MAY BE SUBSTITUTED BY A HALOGEN ATOM, A LOER ALKYL GROUP, A LOWER ALKOXY GROUP OR AN ARHY; GROUP, WHICH GROUP MAY IN TURN BE SUBSTITUTED BY HALOGEN, LOWER ALKYL OR LOWER ALKOXY; R1 STANDS FOR LOWER ALKYL, HYDROXYALKYL, OR SULFOALKYL; R2 IS HYDROGEN OR LOWER ALKYL, A DESIGNATES ALKYLENE, -(CH2)2-O-(CH2)2-OR-(CH2)2-O CH2CH(OH) CH2-;AND N1 AND N2 ARE EACH O OR 1.
2. A silver halide photosensitive material for color photography according to claim 1, wherein each of said layers contains a coupler.
3. A silver halide photosensitive material for color photography according to claim 1, wherein said heterocyclic ring nucleus in said general formula is selected from thiazole, benzothiazole, selenazole, and benzoselenazole.
4. A silver halide photographic material for color photography according to claim 1, wherein said blue-sensitive emulsion layer contains a yellow coupler, said green-sensitive emulsion layer contains a magenta coupler, and said red-sensitive emulsion layer contains a cyan coupler.
5. A silver halide photosensitive material for color photography according to claim 4, wherein said heterocyclic nuclei in said sensitizing dye are each selected from thiazole, benzothiazole, selenazole, and benzoselenazole.
US3847613A 1972-01-24 1973-01-22 Silver halide photosensitive materials for color photography Expired - Lifetime US3847613A (en)

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US3847613A Expired - Lifetime US3847613A (en) 1972-01-24 1973-01-22 Silver halide photosensitive materials for color photography

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JP (1) JPS5037538B2 (en)
DE (1) DE2303204A1 (en)
GB (1) GB1366623A (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976492A (en) * 1974-07-25 1976-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions
US3985563A (en) * 1974-09-09 1976-10-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3986878A (en) * 1974-09-04 1976-10-19 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3988155A (en) * 1974-09-04 1976-10-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4018610A (en) * 1974-07-26 1977-04-19 Fuji Photo Film Co., Ltd. Supersensitized silver halide photographic emulsion
FR2379577A1 (en) * 1977-02-02 1978-09-01 Polaroid Corp thiacyanine-betaine dye for sensitization of photographic emulsions blue
US4147547A (en) * 1975-03-29 1979-04-03 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4818671A (en) * 1986-07-31 1989-04-04 Konishiroku Photo Industry Co., Ltd. Rapidly processable silver halide color photosensitive material
US4828969A (en) * 1985-05-01 1989-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
US5024928A (en) * 1988-07-19 1991-06-18 Minnesota Mining And Manufacturing Company Silver halide multilayer color reversal photographic material having improved color reproducibility
US5047311A (en) * 1984-05-29 1991-09-10 Mitsubishi Paper Mills Ltd. Panchromatic silver halide photographic element
US5250544A (en) * 1990-07-10 1993-10-05 Adir Et Compagnie New piperidine tetrahydropyridine and pyrrolidine compounds
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US5474887A (en) * 1994-04-15 1995-12-12 Eastman Kodak Company Photographic elements containing particular blue sensitized tabular grain emulsion
US5576157A (en) * 1994-04-15 1996-11-19 Eastman Kodak Company Photographic element containing emulsion with particular blue sensitivity
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
US20090247579A1 (en) * 2006-02-21 2009-10-01 Cancer Research Technology Limited 2-[3h-thiazol-2-ylidinemethyl]pyridines and related compounds and their use

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JPS5180224A (en) * 1975-01-07 1976-07-13 Konishiroku Photo Ind Harogenkaginkaraashashinkankozairyo
JPS5516284B2 (en) * 1975-03-17 1980-05-01
JPS599900B2 (en) * 1975-03-29 1984-03-06 Konishiroku Photo Ind
JPS5515019B2 (en) * 1976-07-08 1980-04-21
JPS6114503B2 (en) * 1980-07-07 1986-04-18 Fuji Photo Film Co Ltd
JPH0456299B2 (en) * 1982-12-13 1992-09-08 Konishiroku Photo Ind
EP0197202B1 (en) * 1985-04-09 1990-04-18 AGFA-GEVAERT naamloze vennootschap Photographic silver complex diffusion transfer reversal process
JP2700794B2 (en) * 1988-02-24 1998-01-21 コニカ株式会社 Silver halide photographic light-sensitive material
EP0625726B1 (en) * 1993-05-11 2000-08-09 Fuji Photo Film Co., Ltd. Methine compound and silver halide photographic material comprising the same
DE19841985A1 (en) * 1998-09-03 2000-03-09 Schering Ag New heterocyclic alkanesulfonic and alkane carboxylic acid derivatives are VEGF receptor blockers useful in treatment of e.g. psoriasis, rheumatoid arthritis, stroke, tumors and endometriosis

Citations (4)

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Publication number Priority date Publication date Assignee Title
US2170803A (en) * 1934-08-11 1939-08-29 Eastman Kodak Co Photographic sensitizing dyes and their preparation
US2231659A (en) * 1939-05-09 1941-02-11 Eastman Kodak Co Polymethine dye intermediates
US2921067A (en) * 1957-04-03 1960-01-12 Eastman Kodak Co Method of making carbocyanine and merocarbocyanine spectral sensitizing dyes
US3149105A (en) * 1961-09-14 1964-09-15 Eastman Kodak Co Novel synthesis of cyanines and merocyanines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170803A (en) * 1934-08-11 1939-08-29 Eastman Kodak Co Photographic sensitizing dyes and their preparation
US2231659A (en) * 1939-05-09 1941-02-11 Eastman Kodak Co Polymethine dye intermediates
US2921067A (en) * 1957-04-03 1960-01-12 Eastman Kodak Co Method of making carbocyanine and merocarbocyanine spectral sensitizing dyes
US3149105A (en) * 1961-09-14 1964-09-15 Eastman Kodak Co Novel synthesis of cyanines and merocyanines

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976492A (en) * 1974-07-25 1976-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions
US4018610A (en) * 1974-07-26 1977-04-19 Fuji Photo Film Co., Ltd. Supersensitized silver halide photographic emulsion
US3986878A (en) * 1974-09-04 1976-10-19 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3988155A (en) * 1974-09-04 1976-10-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3985563A (en) * 1974-09-09 1976-10-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4147547A (en) * 1975-03-29 1979-04-03 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
FR2379577A1 (en) * 1977-02-02 1978-09-01 Polaroid Corp thiacyanine-betaine dye for sensitization of photographic emulsions blue
US4250244A (en) * 1977-02-02 1981-02-10 Polaroid Corporation Thiacyanine betaine blue sensitizing dyes
US5047311A (en) * 1984-05-29 1991-09-10 Mitsubishi Paper Mills Ltd. Panchromatic silver halide photographic element
US4828969A (en) * 1985-05-01 1989-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material
US4818671A (en) * 1986-07-31 1989-04-04 Konishiroku Photo Industry Co., Ltd. Rapidly processable silver halide color photosensitive material
US5024928A (en) * 1988-07-19 1991-06-18 Minnesota Mining And Manufacturing Company Silver halide multilayer color reversal photographic material having improved color reproducibility
US5250544A (en) * 1990-07-10 1993-10-05 Adir Et Compagnie New piperidine tetrahydropyridine and pyrrolidine compounds
US5278185A (en) * 1990-07-10 1994-01-11 Adir Et Compagnie Piperidine, Tetrahydropyridine and pyrrolidine compounds
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US5474887A (en) * 1994-04-15 1995-12-12 Eastman Kodak Company Photographic elements containing particular blue sensitized tabular grain emulsion
US5576157A (en) * 1994-04-15 1996-11-19 Eastman Kodak Company Photographic element containing emulsion with particular blue sensitivity
US5582960A (en) * 1995-02-17 1996-12-10 Eastman Kodak Company Photographic print material
US20090247579A1 (en) * 2006-02-21 2009-10-01 Cancer Research Technology Limited 2-[3h-thiazol-2-ylidinemethyl]pyridines and related compounds and their use

Also Published As

Publication number Publication date Type
DE2303204A1 (en) 1973-08-16 application
JPS5037538B2 (en) 1975-12-03 grant
GB1366623A (en) 1974-09-11 application
JPS4878930A (en) 1973-10-23 application

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AS Assignment

Owner name: KONICA CORPORATION, JAPAN

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:KONISAIROKU PHOTO INDUSTRY CO., LTD.;REEL/FRAME:005159/0302

Effective date: 19871021