US3619198A

US3619198A - Silver halide emulsions containing hydroxy substituted alicyclic compounds

Info

Publication number: US3619198A
Application number: US834880A
Authority: US
Inventors: Nobuo Yamamoto; Akikazu Mikawa; Minoru Sonoda
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1968-06-19
Filing date: 1969-06-19
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: DE1930816B2; DE1930816A1; GB1244566A; BE734697A; FR2011212A1

Abstract

Silver halide photographic emulsions containing antifogging, sensitizing hydroxy-substituted alicyclic compounds. The present invention relates to a silver halide photographic emulsions and a process for the preparation thereof. More particularly, the present invention relates to a silver halide photographic emulsion containing a compound which has simultaneous sensitizing and antifogging effects and a process for the preparation thereof. Hitherto, in order to increase the sensitivity of a silver halide photographic emulsion, chemical ripening, e.g., sulfur sensitization, reduction sensitization or gold sensitization has been carried out during the preparation of the emulsion. In addition, various sensitizers have been added to the final photographic emulsion after chemical ripening. However, it is known that fog increases as the sensitivity of the silver halide photographic emulsion is increased. Such fog is a fatal defect in photographic light-sensitive materials. Many attempts have been previously made to remove such fog. Many attempts have been previously made to remove such fog. For instance, an antifoggant or stabilizer has been added to the final silver halide photographic emulsion for reducing fog formation after chemical ripening. However, the fog cannot be completely removed by this method, and other defects sometimes result from the use of additives which have an adverse effect upon photographic properties. An object of this invention, therefore, is to provide sensitized silver halide photographic emulsions having decreased fog and a process for the production thereof. This object is attained by adding an alicyclic compound having two or more hydroxy groups attached either directly to the ring or to a side chain to a silver halide photographic emulsion. Preferred alicyclic compounds for use in the present invention are substituted alicyclic hydrocarbons having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl. Typical alicyclic compounds as described above to be used in the present invention are as follows:

The compounds of this invention act as both sensitizer and antifoggant and provide superior sensitizing effects as compared with sensitizers used hitherto. Further, these compounds have the ability to decrease the fog, which would otherwise increase as the sensitivity increased. Accordingly, the silver halide emulsions of this invention have remarkably low fog formation and excellent sensitivity as compared with known prior art emulsions. The compounds of this invention may be added to the silver halide emulsion after chemical ripening together with other additives in accordance with conventional practice, or they may be added to the silver halide emulsion after conventional physical ripening. Notably excellent results are obtained when the addition takes place at the beginning of chemical ripening. The amount of the compound employed depends upon the result desired, the degree of ripening, kind of emulsion, etc. Amounts of about 2-100 g., and especially 5-50 g. per mol of silver halide present are preferred. No adverse effects on the photographic properties of the film result from the addition of these compounds in combination with other photographic additives usually employed, such as optical sensitizers, coating aids, hardening agents and plasticizers. Further, these compounds may be used in any kind of silver halide photographic emulsion, such as orthochromatic emulsions, panchromatic emulsions, emulsions for X-ray photographic films, emulsions for photographic papers and color photographic films, with any conventional binder such as gelatin and polyvinyl alcohol, and on any kind of support such as glass, cellulose triacetate film, polyethylene terephthalate film and barita paper. The invention will be illustrated by the following examples wherein AgX is total silver halide present.

Description

United States Patent [72] inventors v Nobuo Yamamoto;

Akilrazu Mikawa; Minoru Sonoda, all of Kamagawa, Japan [21 Appl. No. 834,880

[22] Filed June 19, 1969 [45] Patented Nov. 9, 1971 [73] Assignee Fuji Photo Film Co., Ltd.

Kanagawa, Japan [32] Priority June 19, 1968 [33] Japan [54] SILVER HALIDE EMULSIONS CONTAINING HYDROXY SUBSTITUTED ALICYCLIC COMPOUNDS 8 12 Claims, No Drawings [52] U.S. Cl 96/107, 96/ l 09 [5 1] Int. Cl G03c 1/28, G03c 1/34 [50] Field of Search 96/109, 107

[56] References Cited OTHER REFERENCES Chemical Abstracts vol. 59, l963 ,column 159a.

Primary Examiner-Norman G. Torchin Assistant Examiner-R. Fichter Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: Silver halide photographic emulsions containing antifogging, sensitizing hydroxy-substituted alicyclic compounds.

SILVER HALIDE EMULSIONS CONTAINING HYDROXY SUBSTITUTED ALICYCLIC COMPOUNDS The present invention relates to a silver halide photographic emulsions and a process for the preparation thereof. More particularly, the present invention relates to a silver halide photographic emulsion containing a compound which has simultaneous sensitizing and antifogging effects and a process for the preparation thereof.

Hitherto, in order to increase the sensitivity of a silver halide photographic emulsion, chemical ripening, e.g., sulfur sensitization, reduction sensitization or gold sensitization has been carried out during the preparation of the emulsion. In addition. various sensitizers have been added to the final photographic emulsion after chemical ripening.

However, it is known that fog increases as the sensitivity of the silver halide photographic emulsion is increased. Such fog is a fatal defect in photographic light-sensitive materials. Many attempts have been previously made to remove such fog. Many attempts have been previously made to remove such fog. For instance, an antifoggant or stabilizer has been added to the final silver halide photographic emulsion for reducing fog formation after chemical ripening.

However, the fog cannot be completely removed by this method, and other defects sometimes result from the use of additives which have an adverse effect upon photographic properties.

An object of this invention, therefore, is to provide sensitized silver halide photographic emulsions having .decreased fog and a process for the production thereof. This object is attained by adding an alicyclic compound having two or more hydroxy groups attached either directly to the ring or to a side chain to a silver halide photographic emulsion.

Preferred alicyclic compounds for use in the present invention are substituted alicyclic hydrocarbons having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl.

Typical alicyclic compounds as described above to be used in the present invention are as follows:

Compound (1) H,C-CH,

CH-OH 1,2-eyclopentanedlol I;CC

Compound (2) Compound (3) CH-OH l-methy12,3-eyclopentanediol H C-CH 6H Compound (4) Compound (6) C H-C H;

11,0 CH-OH 1,2-cyclohoxanedlol on cu Compound (7) GHQ-CH1 mo cit-0H 1,3-cyclohexanediol CHCHg Compound (8) CII CH I ()IIC CH-OH (015-)lA-cyclohexanediol CH C g Compound (9) (Ill -CH,

llO IIC CII-OH (trans-) 1,4 cyololmxunedimethnnnl CH -CH,

Compound (10) CH -CH,

HOOH -HC CH-CHgOH 1,4-cyclohexanedimethanol Compound (11) C x- 2 CH2 CH, C l-rnethyI-l,2-eyclohexandiol CH -CH OH OH Compound (12) GIL-CH,

H,C\ CIICH,OH Z-hydroxymethylcyclohexanol CHrfiJfi Compound (13) g on E oil-0H, 5 I1 0 CH-OII 1,3,5-cyclohexanetrlol CHC 1 The compounds of this invention act as both sensitizer and antifoggant and provide superior sensitizing effects as compared with sensitizers used hitherto. Further, these compounds have the ability to decrease the fog, which would otherwise increase as the sensitivity increased. Accordingly, the silver halide emulsions of this invention have remarkably low fog formation and excellent sensitivity as compared with known prior art emulsions.

The compounds of this invention may be added to the silver halide emulsion after chemical ripening together with other additives in accordance with conventional practice, or they may be added to the silver halide emulsion after conventional .physical ripening. Notably excellent results are obtained when the addition takes place at the beginning of chemical ripening. The amount of the compound employed depends upon the result desired, the degree of ripening, kind of emulsion, etc.

Amounts of about 2-l00 g., and especially 5-50 g. per mol of silver halide present are preferred.

Noadverse effects on the photographic properties of :the

film result from the addition of these compounds in combina- 7 tion with other photographic additives usually employed, such as optical sensitizers, coating aids, hardening agents and plasticizers.

Further, these compounds may be used in any kind of silver halide photographic emulsion, such as orthochromatic emulsions, panchromatic emulsions, emulsions for X-ray photographic films, emulsions for photographic papers and color photographic films, with any conventional binder such as gelatin and polyvinyl alcohol, and on any kind of support such as glass. cellulose triacetate film, polyethylene terephthalate film and barita paper.

The invention will be illustrated by the following examples wherein AgX is total silver halide present.

EXAMPLE 1 into a gelatino silver iodobromide emulsion not yet chemically sensitized (1.5 percent mol percent Agl and 150 g. of gelatine per 1 mol AgX 1,2-cyc1opentanediol (Compound 1) 1-methyl-2,3-cyclopentanediol (Compound 3), l,4-cyclohexane dimethanol (Compound or l-methyl-1,2-cyclohexanediol (Compound 1 l was added. Then 2 g. of a sensitizing gelatin which contains a natural sulfur sensitizer, 0.3 mg. ofi HAuCl,-4H O as the gold sensitizer and an aqueous solution of 50 mg. of KSCNS per 1 mol of silver were added in the desired; amount. The second ripening was then carried out with stir-i ring at 53 C. for a prescribed period of time. After addingi chrome alum and saponin into thus resulting emulsion, it was; applied to cellulose triacetate film and dried. The same photo-E graphic film as described above but not including any additive of this invention was prepared as a control sample for comparison. These photographic films were exposed to light by the NSG 11 type sensitometer and treated with a developing solution having the following composition at C. for 4 minutes.

Composition of the Developing Solution N-methyl-p-aminophenol sulfate 4.0 g. Anhydrous sodium sulfite 60.0 g. Hydroquinone 10.0 g. Anhydrous sodium carbonate 53.0 g. Potassium bromide 2.5 g. Water to make 1 liter Results obtained are shown in the following table. The speed was calculated from the amount of exposure required to: produce an optical density of 0.3 above fog, and was shown relatively on the basis of 100 at 125 minutes of ripening of the control.

Compound Concentration Ripening Ripening Ripening g./mol of AgX I min. 140 min. 155 minutes speed fog speed fog speed fog None (control 100 0.09 107 0.ll 137 0.141 (1) l7.3 115 0.07 141 0.09 050 0.11 1 (3) 19.7 117 0.07 139 0.09 156 0.11 (10) 20.4 121 0.05 149 0.06 165 007 (II) 22.5 125 0.06 147 0.07 160 0.08

It is clear from the above table that the speed increases and the fog decreases in the silver halide photographic emulsions of this invention as compared with the control emulsion.

EXAMPLE 2 Into a gelatino silver iodobromide emulsion for high sensitivity negative film (7 mol percent Agl and 200 g. ofgelatin per 1 mol of AgX), 1,2-cyclohexanediol (Compound 6), 1,3- cyclohexanediol (Compound 7), cis-l,4-cyclohexanediol (Compound 8) or trans-l,4-cyclohexanediol (Compound 9) was added. Then sulfur and gold sensitizing treatments were carried out at 52 C. Each of the resulting mixtures was applied to a cellulose acetate film so that the coating amount of silver was mg/100 cm?. The same photographic film as described above but not containing an additive of this invention was prepared as a control sample for comparison.

These photographic films were exposed to light by the NSG 11 type sensitometer and developed using a developing solution having the following composition at 20 C. for 7 minutes. 5

Composition of the Developing Solution N-methyl-p-aminophenol sulfate Anhydrous sodium sulfite Hydroquinone 5.0 g. Borax 2.0 g. Water torn ke I 1 liter The results thus obtained are shown in the following table. The speed was calculated from the amount of exposure required to produce an optical density of 0.3 above fog, and

' was shown relatively onthe basis of 100 at minutes ripenanediol,

ing of the control.

Coneon- Ripenlng Riponing Ripening tratlon, 50 min. 65 min. 70 mln. gJmol.

0 AgX Speed Fog Speed Fog Speed Fog N one (control) 0. 10 0.17 131 0. 30 Compound 0. l9. 4 103 0. 06 131 0. 07 137 0. 10 Compound 7. 19. 4 105 0. 07 131 0. 07 140 0. 11 Compound 8. 19.4 103 0. 06 0. 07 0. 11 19.4 013 0.06 129 0. 08 138 0.12

Compound 0.

it is clear from the above table that the speed increases and the fog decreases in the silver halide photographic emulsions produced by the process of this invention.

EXAMPLE 3 A gelatino silver iodobromideemulsion for a high sensitivity radiographic film (1.5 mol percent Agl and g. of gelatin per 1 mol of AgX) subjected to sulfur and gold sensitizations were prepared. Just before application of the emulsion to a support, 2-hydroxymethyl hexanol (Compound 12) or 1,3,5- cyclohexanetriol (Compound 13) was added to the emulsion, and then chrome alum and saponin were added thereto. The emulsion was then applied to a cellulose triacetate film and dried. The same photographic film as described above but not containing an additive of this invention was produced as a control for comparison. These films were exposed to light and developed as in example 1. The results were shown in the following table, in which the relative speed based on a speed of 100 for the control was calculated from the exposure required to provide an optical density of 0.3 above fog.

Compound Concentration Speed Fog g-lmol of AgX (fog 0.3)

None (control) 100 2.13 0.50

being selected from the group consisting of hydroxy and hydroxy-alkyl.

2. The silver halide photographic emulsion of claim 1 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol, l-methyl-2,3-cyclopentancdiol, 1,3- cyclopentanediol, Z-hydroxymethyl cyclopentanoL. 1,2- cyclohexanediol, 1,3-cyclohexanediol, cis-l ,4-cyclohextrans-1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1-methyl-l,Z-cyclohexanediol, 2-hydroxymethyl-cyclohexanol and 1,3,5-cyclohexanetriol.

3. The silver halide photographic .emulsion of claim 1 wherein said substituted alicyclic hydrocarbon is present in the range of from about 2 to 100 g. per mole of silver halide.

4. The silver halide photographic emulsion of claim 1 wherein said silver halide photographic emulsion is a silver iodobromide emulsion.

5. A process for preparing a silver halide photographic emulsion which comprises adding a sensitizing amount of a substituted alicyclic hydrocarbon having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl, to a physically ripened silver halide emulsion prior to chemical ripening.

6. A photographic element comprising a support having coated thereon at least one silver halide emulsion layer containing a sensitizing amount of a substituted alicyclic hydrocarbon having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl.

7. The process of claim 5 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of l,2-cyclopentanediol, l,2-cyclobutanediol, l-methyl-2,3- cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol, l,2-cyclohexanediol, 1,3-cyclohexanediol, cisl,4-cyclohexanediol, transl ,4-cyclohexanediol, 1,4- cyclohexanedimethanol, l-methyl-l,2-cyclohexanediol, 2-

hydroxymethyl-cycloehexanol and 1,3,5-cyclohexanetriol.

8. The process of claim 5 wherein said substituted alicyclic hydrocarbon is present in the range of from about 2 to 100 g. per mole of silver halide.

9. The process of claim 5 wherein said silver halide photographic emulsion is a silver iodobromide emulsion.

10. The photographic element of claim 6 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of l,2-cyclopentanediol, l,2-cyclobutanediol, l-methyl-2,3-cyclopentanediol, l ,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol, l,2-cyclohex-

Claims

2. The silver halide photographic emulsion of claim 1 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol, 1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1-methyl-1, 2-cyclohexanedioL, 2-hydroxymethyl-cyclohexanol and 1,3,5-cyclohexanetriol.
3. The silver halide photographic emulsion of claim 1 wherein said substituted alicyclic hydrocarbon is present in the range of from about 2 to 100 g. per mole of silver halide.
4. The silver halide photographic emulsion of claim 1 wherein said silver halide photographic emulsion is a silver iodobromide emulsion.
5. A process for preparing a silver halide photographic emulsion which comprises adding a sensitizing amount of a substituted alicyclic hydrocarbon having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl, to a physically ripened silver halide emulsion prior to chemical ripening.
6. A photographic element comprising a support having coated thereon at least one silver halide emulsion layer containing a sensitizing amount of a substituted alicyclic hydrocarbon having four to six carbon atoms in the ring, wherein the substituents are selected from the group consisting of hydrogen, alkyl having one to four carbon atoms, hydroxy and hydroxy-alkyl having one to four carbon atoms, at least two of said substituents being selected from the group consisting of hydroxy and hydroxy-alkyl.
7. The process of claim 5 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of 1, 2-cyclopentanediol, 1,2-cyclobutanediol, 1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1-methyl-1,2-cyclohexanediol, 2-hydroxymethyl-cyclohexanol and 1,3,5-cyclohexanetriol.
8. The process of claim 5 wherein said substituted alicyclic hydrocarbon is present in the range of from about 2 to 100 g. per mole of silver halide.
9. The process of claim 5 wherein said silver halide photographic emulsion is a silver iodobromide emulsion.
10. The photographic element of claim 6 wherein said substituted alicyclic hydrocarbon is a member selected from the group consisting of 1,2-cyclopentanediol, 1,2-cyclobutanediol, 1-methyl-2,3-cyclopentanediol, 1,3-cyclopentanediol, 2-hydroxymethyl cyclopentanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1-methyl-1,2-cyclohexanediol, 2-hydroxymethylcyclohexanol and 1,3,5-cyclohexanetriol.
11. The photographic element of claim 6 wherein said substituted alicyclic hydrocarbon is present in the range of from about 2 to 100 g. per mole of silver halide.
12. The photographic element of claim 6 wherein said silver halide photographic emulsion is a silver iodobromide emulsion.