|Publication number||US3635721 A|
|Publication date||Jan 18, 1972|
|Filing date||Dec 4, 1967|
|Priority date||Dec 3, 1966|
|Also published as||DE1597589A1, DE1597589C2|
|Publication number||US 3635721 A, US 3635721A, US-A-3635721, US3635721 A, US3635721A|
|Inventors||Hinata Masanao, Misu Hiroshi, Sato Akiro, Shiba Keisuke|
|Original Assignee||Fuji Photo Film Co Ltd|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (2), Non-Patent Citations (1), Referenced by (14), Classifications (17)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Milo oi; all,
 SIPIECWALLW SIENMTHZIEIW PHOTOORAPHHC siwmi HALWE IEMFULEHUNS  Inventors: Alitiro Soto; lllliroslhi Misti; lifieisulte Shilm;
Mastmno Minute, all of Kanagawa, Japan  Assignee: Fuji Photo Film Co, Ltd., Kanagawa,
Japan  Filed: Dec. 4, 11967  Appl. No.: 687,469
 Foreign Application Priority Date Dec. 3, 1966 Japan ..41/79255  Ufi. Cll ..96/126, 96/133  Int. Cl. .JGmc 11/28, G03c 1/20  Field oil Search ..96/l04, 126
 References Cited UNITED STATES PATENTS 2,933,390 4/1960 McFall et a1. ..96/104 X FOREIGN PATENTS OR APPLICATIONS 168,596 11/1965 U.S.S.R. ..96/104 OTHER PUBLICATIONS I-Iamer, The Cyanine Dyes and Related Compounds, (1964), p. 207.
Primary Examiner-William D. Martin Assistant Examiner-David Cohen AtwrneySughrue, Rothwell, Mion, Zinn & Macpeak 57 AnsrnAcr A photographic silver halide emulsion composition comprising a sensitizing dye shown by general formula (I) alkyl group; X represents an anion, n stands for 1 or 2; and m stands for l or 2, and a compound shown by general formula R3-Z( INHA-NH-I TZR3 V Y 14 R4 (ll) S 03M S 03M S 03M @CONH S aM wherein M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium. and an amino group.
6 Claims, No Drawings SPECTRALLY SENSllTlZlED PHOTOG RAH-11M: SILVER HALHIDE EMULSEONS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to spectrally sensitized photographic silver halide emulsions and more particularly to supersensitized photographic silver halide emulsions.
2. Description of the Prior Art It is well known that by incorporating a sensitizing dye in a silver halide emulsion in the case of producing a photographic silver halide emulsion, the wavelength region of light-sensitivity ofthe llilVCfl' halide emulsion its enlarged and the silver halide emuluitm in Mpectrally sensitized. Alan, it is known that the menaitivity of u silver halide emulsion sensitized by a definite sensitizing dye may be varied according to the type of emulsion into which the sensitizing dye is introduced. Furthermore, the sensitivity of a definite emulsion sensitized by a definite sen sitizing dye can be varied by changing the properties of the emulsion. For instance, the sensitivity of a silver halide emulsion can be increased by increasing the silver ion concentration or by reducing the hydrogen ion concentration or by a combination thereof. However, the silver halide emulsion sensitized in such a way has the disadvantage that the preservability thereof is generally bad.
There is, however, a so-called supersensitizing action, that is, a phenomenon of increasing the sensitivity of a silver halide emulsion by incorporating in the emulsion a compound along with a sensitizing dye without changing the properties of the emulsion as mentioned above, e.g., without changing the silver ion concentration and the hydrogen ion concentration of the emulsion. The compound which is used together with the sen sitizing dye is generally called a supersensitizer.
As the spectral sensitizer for a photographic silver halide emulsion, there are usually used dicarbocyanines. Among them, a mesosubstituted dicarbocyanine has a merit in that the formation of fog in a silver halide emulsion sensitized by it is very low as compared with the case of using mesounsubstituted dicarbocyanines. In some cases, however, the addition of the mesosubstituted dicarbocyanine to a silver halide emulsion is accompanied by a reduction in sensitivity. Particularly in the case of using a dicarbocyanine, the mesoposition of which has been substituted with a halogen, the sensitivity of the silver halide emulsion containing the dicarbocyanine is reduced markedly.
However, if it is possible to increase the sensitivity of a silver halide emulsion by incorporating therein the aforesaid spectral sensitizer together with a certain supersensitizer, a photographic silver halide emulsion having high sensitivity and low fog can be obtained, and this is very desirable and useful for practical purposes.
Thus, an object of the present invention is to provide a photographic silver halide emulsion in which a mesosub stituted carbocyanine and a specific supersensitizer, as mentioned below, have been incorporated to improve the sensitivity thereof and reduce the formation of fogs. Another object of the present invention is to provide a photographic light-sensitive element having high sensitivity and low fog.
SUMMARY OF THE INVENTION These and other objects of this invention can be achieved by incorporating in a photographic silver halide emulsion the mesosubstituted carbocyanine shown by the following general formula (I) together with the compound shown by the following general formula (II):
wherein Y and Y, each represents a nonmetallicatomic group necessary for forming a heterocyclic ring. such as, a thiazole, a benzothiazole, a nuphthothiazole, naphthoselenazole, a selenazole, a benzoselenazole, a benzoxazole, a naphthoxazole, an oxazole, a Z-quinoline, a 4-quinoline, an indolenine and the like; R and R, each represents an alkyl group, such as, an ethyl group, a propyl group, and the like; a substituted alkyl group, such as, a 2-hydroxyethyl group, a Z-methoxyethyl group, a carboxymethyl group, a Zcarboxyethyl group, a 3- carboxypropyl group, a 4-carboxybutyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a carbomethoxymethoxy group, a carboethoxymethyl group, a carbomethoxyethyl group, a carhoethoxyethyl group, and the like; an urylgroup. an ullyl group; or an aralkyl group; R, represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and the like; or an alkyl group such as a methyl group, an ethyl group, a'propyl group and the like; X represents an anion; n is l or 2; and m is l (in the case of forming an intramolecular salt) or2; and
wherein Z represents CH or N; R and R, each represents a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, an arylthio group, an aryl group, an amino group, an alkylamino group, an arylamino group, or an aralkylamino group; and A represents a group selected from the following:
I 5 our s 03H DETAILED DESCRlPTlON OF THE lNVENTlON Typical examples of the mesosubstituted dicarbocyanines used in the present invention are shown below together with methods of preparing them.
PREPARATION 1 Preparation of mesoethyl-3, 3-diethylthiadicarbocyanine iodide;
in a mixture of ml. of acetic anhydride and 1 ml. of acetic acid there were dissolved 1.5 g. of 2-methyl-3-ethylbenzothiazolium iodide and 0.6 g. of l-ethyl-2-anilinoacrolein anil, and they were reacted by heating the system for 2 minutes under refluxing. After cooling, the crystal thus precipitated was recovered by filtration. The crystal was washed with water and recrystallized from ethanol to provide 0.5 g. of dye (I-l) having a melting point of 240 C. (d). The absorption maximum of the dye in methanol was 648 my" By the same methods as above, the mesosubstituted carbocyanines shown by formulas (I-2), (l-3 (I-4) and (L5) can be prepared.
In a mixture of 20 ml. of pyridine and 5 ml. of acetic acid were dissolved 2.5 g. of 3-carboXymethyl-5,6-dimethylbenzothiazolium bromide and l g. of l-ethyl-2-anilinoacrolein anil. The solution was heated for 3 minutes under refluxing and 4 ml. of triethanolamine was added to the solution. Thereafter, they were reacted by heating the system for 2 minutes under refluxing. After cooling, water was added to the product and the crystal precipitated was recovered by filtration and recrystallized from methanol to provide 0.3 g. of dye (l-6) having a melting point of 194 C. (d) and an absorption maximum in methanol of 663 mu.
The same procedure as in the case of preparing dye (H) was repeated using, however, l-chloro-2-anilinoacrolein anil instead of l-ethyl-2-anilinoacrolein anil to provide dye (l-7) having a melting point of 252 C. (d), and an absorption maximum in methanol of 646 my The same procedure as in the case of preparing dye (H) was repeated using l-bromo-2-anilinoacrolein anil instead of l-ethyl-2-anilinoacrolein anil to provide dye (l-8) having a melting point of 221 C. (d), and an absorption maximum in methanol of 646 my.
SOaNa OzNa OaNa S OaNa OaNa S OaNa OZNE CHaCH- OsNa Among the compounds shown by general formula (11), the compounds in which Z is 1I t l 1atis, the compounds hav' ing an S-triazine nucleus may be prepared by known methods. Also, among the compounds in which Z is -CH=, that is, the compounds having a pyrimidine nucleus, those compounds wherein R and R are halogen atoms or various amino groups, or the compounds wherein R or R is bonded to the pyrimidine nucleus by an ether bond or a thioether bond may be prepared by procedures of the type shown in the following examples. 7
PREPARATION 5 Preparation of the compound shown by the formula (11-25) as shown above:
Mixed with m1. of acetone were 1 1.0 g. of 2,4,6- trichloropyrimidine and 12.4 g. of sodium 4,4'-diaminostilbene-2,2'-disulfonate and the mixture was stirred at 55-65 C. Hydrochloric acid formed during reaction was neutralized by the addition of a 10 percent aqueous sodium carbonate solution whereby the reaction mixture was maintained at the state of from neutral to weak acid. After the reaction was finished, the reaction mixture was ice-cooled to form a crystal of compound (II-25 which was recovered by filtration.
PREPARATION 6 Preparation of the compound shown by formula (ll-23 A mixture of 14.1 g. of sodium 4,4-
bis(dichloropyrimidinylamino)-stilbene-2,2'-disulfonate, 4.4 g. of thiophenol, and 1.6 g. of sodium hydroxide was heated under refluxing in a solvent mixture of 70 ml. of water and 20 ml. of dioxane for about 2.5 hours. After cooling, the precipitate thus formed was removed by filtration and from the filtrate was removed dimethylformamide by distillation under a reduced pressure. The residue thus obtained was dissolved in a solvent mixture of water and acetone and about 5 ml. of concentrated hydrochloric acid was added and the crystal thus formed was recovered by filtration. The crystal of compound (II-23) was washed with water and dried.
PREPARATION 7 Preparation of the compound shown by formula (11-24):
A mixture of 14.1 g. of sodium 4,4'-bis-(dichloropyrimidinyl)-stilbene-2,2-disulfonate, 4.4 g. of thiophenol and 1.6 g. of sodium hydroxide was heated under refluxing in a solvent mixture of 70 m1. of water and 20 ml. of dioxane. After the end of water, about 5 ml. of concentrated hydrochloric acid was added to the reaction mixture to precipitate the product, which was recovered by filtration under suction and washed with water and methanol followed by drying.
The addition amount of the mesosubstituted carbocyanine sensitizing dye used in the present invention is suitably from about 0.002 to 0.2 g. per one gram molecule of silver halide contained in the silver halide emulsion and the addition amount of the super-sensitizer having general formula (11) is suitably from about 0.05 to 10 g. per one gram of silver halide in the silver halide emulsion. Furthermore, the suitable ratio of sensitizing dye (l) to compound (11) is from about 1:2 to 1:200.
Sensitizing dye (1) may be added to a silver halide emulsion by any method well known in this field. Compound (11) may be added to a silver halide emulsion as a solution of the compound in an organic solvent, such as methanol or ethanol. Sensitizing dye (l) and compound (11) are added to a silver halide emulsion prior to coating. Sensitizing dye (1) may be added to a silver halide emulsion before or after the addition of com pound (11) or may be added together with the latter.
1n the silver halide emulsion of this invention, various silver salts may be used such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide and the like. Moreover, to the silver halide emulsion there may be added the usual additives such as a chemical sensitizer, a hardening agent, an antifoggant, a wetting agent, a stabilizer, a plasticizer, a development accelerator, and an antibronzing agent. Also, the silver halide emulsion of this invention may contain a coupler capable of forming dye by color development such as a cyan coupler without affecting the merits of the addition of the compounds of this invention. I V
The photographic silver halide emulsion may be applied to a suitable support, such as a glass plate, a film of a cellulose derivative, a synthetic resin film, a baryta-coated paper and the like.
The invention will further be explained by the following example.
EXAMPLE A silver chlorobromide gelatin emulsion containing 40 mol percent bromine and having incorporated therein the mesosubstituted carbocyanine sensitizing dye (l) was applied to a triacetyl cellulose film base. Also, a silver chlorobromide emulsion having the same silver halide concentration as above and having incorporated therein the sensitizing dye (I) and compound (ll) was applied to a triacetyl cellulose film base. After drying, the photographic light-sensitive films were redexposed to a light source of 2,666 K. in color temperature through Fuji No. 7 Filter (transmitting light having longer wave lengths than 590 my.) and then developed for 6 minutes at C. in the developer having the following composition.
N-Methyl-p-Aminiphenol Sulfate 2.0 g. Hydroquinone 4.0 g. Sodium Sulfite 40 g. Sodium Carbonate (Monohydrate) 28 g. Potassium Bromide l g. Water to make 1,000 ml.
While assuming that the red sensitivity of the silver halide emulsion containing only sensitizing dye (l) is 100, the red sensitivities of the silver halide emulsions of this invention containing various combinations of sensitizing dye (l) and compound (II) were compared, The results are shown in the following table. 1
sensitizing dye (I) Compound (11) Red (mm/gram mol of (mg/gram mol of sensi- Ag halide) Ag halide) tivity Fog [-8 (12) 100 0. 04 l-H (12; .l l-ili $300) 135 0. 04 l-X (l2 ll-ll 301)) 229 0. 04 l-i (u) 100 0. 04 l-l g1!) ll-lH (300) [74 0. 04 l-[ il) I H1 (300) 27!) (l. ()4 l 4 (10). 100 0.04 1 10) ll-IH E300) lili 0. 04 l-4 10) ll-(l 300) 809 (l. 04 l-3 11) 100 0. 05 F3 11) ll-llt (300) 118 0. 04 I-3 11) ll-(l (300) 224 0. 04 I5 l1) 100 0. 04 '1-5 (11; 11-18 (300) 151 0. 04 I-& (11 11-45 (300) 288 0. 04 I-9 (9) 100 0. 04 1-9 (9) 6 (300) 537 0. 04 I-9 (9) 11-4 (300) 380 0. 04 I-9 (9) II-1 (300) 331 0. 04 I-9 (9) 11-7 (300) 389 0. 04 1-7 (9) 11-8 (300) 389 0. 04 1-7 (9) 11-5 (300) 214 0. 04 1-7 (9) 11-2 (300) 389 0. 04 I-7 9) 11-10 (300) 372 0. 04 I-7 (9) 11-11 (300) 347 0. 04 I-7 (9) 11-12 (300) 275 0. 04 I-7 9) 11-13 (300) 372 0. 04 I-7 (9) 11-14 (300) 288 0. 04 I-7 E9) 11-15 (300) 601 0. 04 I-7 9) II16 300) 316 0. 04 1-7 (9) 11-17 (300) 275 0. 04 I-7 59) 11-20 (300) 178 0. 04 I-7 9) 1I-21 (300) 191 0. 04 I-6 (9) 100 0. 05 Hi (9) I16 (300) 130 0. 04 [-2 E13) 100 0. 06 1-2 13) 11-6 (300) 316 0. 04 I-2 213) 11-22 (300) 204 0. 04 I-S 12) 100 0. 04 I-8 (12) 11-23 (300) 204 0. 04 I-7 (9) 100 0. 04 I-7 135 0. 04
What is claimed is:
1. A photographic silver halide emulsion composition comprising a silver halide and a sensitizing dye shown by the following formula wherein Z represents a member selected from the group consisting of CH and N; R and R each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an arylthio group, an aryl group, an amino group, an alkylamino group, an arylamino group and an aralkylamino group; and A represents a memberselected from the group consisting of:
s do? wherein M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amino group.
2. The photographic silver halide emulsion, according to claim 1 wherein said sensitizing dye is incorporated in the silver halide emulsion in an amount of from about 0.002 to 0.2 g. per one gram molecule of the silver halide in said emulsion.
3. The photographic silver halide emulsion according to claim 1 wherein said compound is incorporated in said silver halide emulsion in an amount of from about 0.05 to 10 g. per one gram molecule of the silver halide in the emulsion.
is X- /n-l Iii wherein Y and Y each represents a nonmetallic atomic group necessary for forming a heterocyclic ring; R and R, each represents a member selected-from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, an allyl group and an aralkyl group; R represents an alkyl group; X represents an anion, n stands for l or 2; and m stands for l or 2, and from about 0.05 to grams per 1 gram molecule of said silver halide of a compound shown by the formula wherein Z represents a member selected from the group consisting of CH and N; R and R each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxyl group, an arylorty group, an
arylthio group, an aryl group, an amino group an alkylamino group, an arylamino group and an aralkylamino group; and A represents a member selected from the group consisting of:
S 0 M S 0 M S 0 M -QQ' S 03M S 03M S 03M wherein M represents a member selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, and an amino group, wherein the weight ratio of said sensitizing dye .to said compound varies from I :2 to 1:200.
' l i V V w I w a m a:
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|Citing Patent||Filing date||Publication date||Applicant||Title|
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|EP0843209A1||Nov 13, 1996||May 20, 1998||Imation Corp.||Silver halide emulsion manufacturing method|
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|U.S. Classification||430/576, 544/296, 544/193.2, 544/197, 548/156, 548/121|
|International Classification||C09B23/00, C09B23/08, G03C1/28, G03C1/08, C09B23/01|
|Cooperative Classification||G03C1/28, C09B23/083, C09B23/0016|
|European Classification||C09B23/00B2, G03C1/28, C09B23/08B|