US3850636A - Treatment of silver halide photographic material - Google Patents

Abstract

in which R'' represents -CH2COOM or -CH2CH2OH and M has the same meaning as described.

In a method for the development of an exposed silver halide photographic material including a prehardening treatment with an aldehyde hardener prior to developing, the improvement which comprises treating said silver halide photographic material between said prehardening and said developing with a bath containing a compound represented by the following general formula (I) R-NH2 I. in which R represents -SO3M, -SO2NH2, -CH2COOM or -C(CH2OH)3 and M represents an atom or group capable of imparting water solubility, or the following general formula (II)

Description

United States Patent [191 Shimamura et al.

[ Nov. 26, 1974 TREATMENT OF SILVER HALIDE PHOTOGRAPHIC MATERIAL [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Sept. 24, 1973 [2l] Appl. No.: 399,897

[30] Foreign Application Priority Data Sept. 26, 1972 Japan 47-96466 [52] US. Cl. 96/50 R, 96/50 PT, 96/66 R [51] Int. Cl G03c 5/26 [58] Field of Search..... G03c/5/30; 96/50 PT, 50 R, 96/66, 66.5

[56] References Cited UNITED STATES PATENTS 3 l68,40() 2/1965 Blackmer et al 96/66 3,647,449 3/1972 Malloy 96/50 3,649,281 3/l972 lwano et al. 96/50 PT Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT In a method for the development of an exposed silver halide photographic material including a prehardening treatment with an aldehyde hardener prior to developing, the improvement which comprises treating said silver halide photographic material between said prehardening and said developing with a bath containing a compound represented by the following general formula (l) R-NH l. in which R represents SO M, S() NH CH COOM or C(CH Ol-l) and M represents an atom or group capable of imparting water solubility, or the following general formula (II) NH (II) 7 Claims, No Drawings TREATIVENT OF SILVER I-IALIDE PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION 1. Field of the Invention V This invention relates to a method for developing a silver halide photographic material and, more particularly, it is concerned with a method of removing the fog formed in the hardening treatment of a silver halide emulsion layer.

2. Description of the Prior Art In the case of treating a silver halide photographic material such as a photographic film, a printing paper or a dry plate, in general, a hardening bath is often used prior to development processing. The purpose of hardening is to increase the physical strength of a silver halide photographic emulsion layer and to prevent the emulsion layer from being mechanically and physically damaged during processing. The use of a hardening bath is preferable, in particular, where an emulsion layer has insufficient strength, where the processing is carried out for a long period of time or where a high temperature or high pH treating solution is used. The use of a hardening bath prior to development is ordinarily referred to as a prehardening step." In such a bath an aqueous solution containing at least one hardening agent which hardens gelatin in a photographic emulsion, for example, aldehydes such as formaldehyde, glyoxal, succinaldehyde and glutaraldehyde is used.

A prehardening bath of this kind hardens an emulsion layer effectively but, on the contrary, causes various deleterious effects on photographic properties, for example, an increase of developing fog, a lowering of developing density during reversal development and a change of color forming properties of color formers present in a color light-sensitive material.

As a means for removing these disadvantageous photographic influences due to the prehardening process,

- it is known to provide a neutralizing bath following the prehardening process. For example, U.S. Pat. No.

3,168,400 discloses the use of an aqueous solution of hydroxylamine or hydrazine as a neutralizing bath. According to this method, the above mentioned disadvantages due to the prehardening step can be overcome, but another disadvantage takes place in that the hydroxylamine or hydrazine is carried over into the subsequent developing step. Since water washing is ordinarily not carried out between the neutralizing bath and developing bath in order to simplify the processing, the materials in the neutralizing bath are carried into the developing bath. As is well known in the art, hydroxylamine or hydrazine, each possessing developing action, causes an unevenness in development as it is carried out in a developing bath.

It is an object of the present invention to provide a method for the treatment of a photographic material, whereby good photographic properties are obtained and sufficient physical strength is provided to the silver halide emulsion layer. a

It is another object of the invention to provide a neutralizing bath which does not adversely influence the photographic properties.

SUMMARY OF THE INVENTION We, the inventors, have found as a result of various In the General paints n R is -CH COOM or CH CH OH and M has the same meaning as described above.

DETAILED DESCRIPTION OF THE INVENTION The compounds represented by the above mentioned general formulas (I) and (II) do not possess developing properties by nature, but have the action of removing a hardener of aldehyde type carried over from the prehardening bath to the neutralizing bath so as to prevent the hardener from being present in the subsequent step. While not desiring to be bound by theory, these removal properties possibly arise from the characteristics of the substituents represented by R and R.

Examples of compounds represented by the above described general formulas are as follows:

(I) Sulfamic Acid H NSO H (2) Sulfamide H NSO NH (3) Glycine H NCH COOH (4) tris( Hydroxymethyl I-I NC( CH OH aminomethane (5) lminodiacetic acid HN(CH COOH (6) Diethanolamine HN(CH CH OH) Of the above-recited compounds, glycine ispreferred.

The neutralizing bath used in the method of the invention comprises fundamentally an aqueous solution of one or more compounds represented by the foregoing general formulas. These compounds are generally added to provide a concentration of from about 0.1 to 50 g, preferably 5 to 30 g, per 1,000 ml. The neutralizing bath of the invention can optionally contain a salt, such as sodium sulfate, magnesium sulfate, sodium acetate and sodium phosphate, to prevent swelling of the gelatin in an amount of about 0 to 200 g/liter, preferably about 50 to I00 g/liter, a pH regulator for adjusting the pH such as borax, acetic acid, sodium acetate, sodium carbonate, sulfuric acid or boric acid, a buffering agent, such as an organic acid or salt thereof such as acetic acid, citric acid or phthalic acid, acetic acid sodium acetate, tartaric acid, inorganic materials such as boric acid, sodium metaborate, borax, sodium carbonate, sodium bicarbonate, potassium metaborate etc., in an amount of about 10 to g/liter, alkali halides such as potassium bromide, sodium bromide, so-

dium chloride, etc., and other conventional fog inhibitors such as nitrogen containing heterocyclic compounds such as S-nitrobenzimidazole 6- nitrobenzimidazole or benzotn'azole 5- nitrobenzotriazole and nitrogen containing heterocyclic mercapto compounds such as l-phenyl-S- mercaptotetrazole, mercaptobenzoxazole, thiouracil, methylbenzothiazole, thioketothiazolidine or 2- mercaptobenzimidazole in an amount of about 1 mg to l g/liter and mildew preventing agents, for example, an organic acid an alkali metal salt thereof and an ester thereof such as benzoic acid, sorbic acid, dehydroacetic acid or oxybenzoic acid in an amount of about to 2 g/liter. These additives for a neutralizing bath are disclosed in US. Pat. No. 3,168,400. The neutralizing bath can be used at any pH range but neutral and acidic pH ranges are desirable to obtain better effects. Generally, a pH of about 3 to 7, preferably a pH of about 4 to 6 is used;

In the practice of the invention, any prehardener, developer and fixer compositions, which are well known in the art, can be used and the selections thereof can be freely varied in the present invention by any of skill in the art.

The method of the invention is applicable to the commonly used silver halide photographic materials comprising a conventional silver halide light-sensitive material using as a dispersion medium gelatin or another hydrophilic high molecular weight material on a support member such as glass, cellulose ester films, polyester films and paper as conventionally used in the art.

The present invention is preferably applied to reversal color photographic materials which are processed at a high pH for a long time, for example, as disclosed in US. Pat. Nos. 3,168,400 and 3,582,322, as well as color papers which are preferably processed at a high temperature in a rapid manner.

The present invention is carried out after a prehardening bath, for example, as disclosed in US. Pat. No. 3,168,400 and, after the treatment bath of the invention, the subsequent processings can be carried out in the conventional order using known treatment solutions. Generally, the temperature employed ranges from about 30C to 60C, preferably 32C to 50C, with the time being dependent upon the temperature used.

The method of the invention favourably compares with the methods of the prior art because the method of the invention results in less development fog, does not cause a lowering of the developing density nor a change in the character of color formers in a color photographic material.

The following examples are given to illustrate the invention in greater detail without limiting the same. Unless otherwise indicated, all parts and percents are by weight.

EXAMPLE 1 A black-and-white film comprising a panchromatically sensitized silver iodobromide (AgI: mol%) gelatin emulsion coated onto a cellulose acetate film support at 16 mg/ 100cm was exposed using a sensitometer and then subjected to the following processings:

The processing solutions used in these processings had the following compositions.

Sodium Bisulfite l Formaldehyde (37% aqueous solution) 15 Borax Sodium Sulfate Potassium Bromide 2 Water to Glacial Acetic Acid Sodium Acetate Additive listed below Water to Additive None Sulfamic Acid Glycine tris(Hydroxylmethyl)aminomcthanc lminodiacetic Acid moon Developer Monomethyl-p-aminophenol 5 g (5: sulfate) Hydroquinone 2 Sodium Sulfite Sodium Hydroxide 1 Sodium Carbonate Monohydrate 41 Potassium Bromide 2 Water to 0 Glacial Acetic Acid Water to Fixer Sodium Thiosulfate Sodium Sulfite Water to The photographic properties of test films obtained are shown in Table 1.

Relative sensitivity is represented by the logarithmic value of the reciprocal of the exposure quantity corresponding to a blackened density of fog above 0.l

It can be seen from these properties that the neutralizing baths containing the compounds represented by the foregoing general formulas are superior in preventing developing fog effectively as well as increasing the sensitivity and gamma value. This is true even when water washing is practiced between the prehardening and neutralizing. Where such is omitted as is often the case, the effects of this invention are emphasized to an even greater extent.

Since the use of a prehardening bath is made possible by this neutralizing bath and the physical strengths of the emulsion layer is raised, a high temperature processing can be accomplished without difficulty.

EXAMPLE 2 exposed using sensitometer and then subjected to the 7 following processings:

Processing Temperature Time Prehardening 37C 2 min 30 sec Neutralizing do. 30 sec First Developing do. 3 min First Stopping do. 30 sec Water Washing do. l min Color Developing do. 3 min 30 sec Second Stopping do. 30 sec Water Washing do. I min Bleaching do. I min 30 sec Fixing do. 1 min Water Washing do. l min The compositions of the processing solutions used were as follows:.

Prehardener Formaldehyde (37% aqueous solution) Pyruvic Aldehyde (40%) Sulfuric Acid Sodium Sulfate Potassium Bromide Borax 5 Water to Neutralizing Solution Potassium Bromide 2 l 0 Glacial Acetic Acid 0 Sodium Hydroxide 6 Sodium Sulfate 50 Additive listed below X Water to 0 First Developer Sodium Hexametaphosphate l l-Phenyl-3-pyrazolidone 0 Sodium Sulfite 50. Hydroquinone 6. Sodium Carbonate (monohydrate) 35 Potassium Bromide 2 Potassium Thiocyanate 1 Potassium Iodide (0.1% aqueous solution) Waterto First Stopping Solution and Second Stopping Solution 25 ml 3 g I000 ml Acetic Acid Sodium Acetate Water to Color Developer I Sodium Hexametaphosphate Benzyl Alcohol Sodium Sulfite Trisodium Phosphate Y 4 Potassium Bromide Potassium Iodide (0.1% aqueous solution) Sodium Hydroxide e 99 9-9. Ui OMOOQO -Continued First Stopping Solution and Second Stopping Solution 4-Amino-3-methyl-N-ethyl-N- l0.0 g

methanesulfonamidoethylaniline Sulfate Ethylenediamine 8.0 ml

Water to I000 ml Bleaching Solution Potassium Ferricyanide I00 g Potassium Bromide 30.0 g

Water to I000 ml L gfiw L Sodium Thiosulfate I50 g Sodium Sulfite l0 g Water to I000 ml In the above described processings, an additive represented by the general formula (I) or (II) was added to the neutralizing solution as shown in the following table. 1

Experiment Additives Quantity F None G Sulfamic Acid 20 g/liter H Glycine 20 g/liter L tris(l-lydroxymethyl)- 20 g/liter aminomethane The results obtained are tabulated'below.

Maximum Density Experiment Red Green Blue F 3.52 2.98 3.08 G 3.34 3.12 3.24 H 3.78 3.09 3.19

As is evident from the results in this table, the maximum density was increased by the addition of the compound of theinvention, represented by thegeneral formula (I) or (II), without contamination and other adverse infiuences upon the photographic properties such as effective sensitivity.

EXAMPLE 3 Examination of the influence on photographic properties was carried out when a neutralizing solution was added to the first developer composition as described in Example 2. 5 percent of each of three neutralizing solutions (one containing sulfamic acid as in Example '2 (Experiment G), one containing 20 g/Iiter of hydrazine sulfate as known in the art (Experiment J) and onecontaining no additive (Experiment F)) was added to the first developer composition. The photographic emulsions, exposure conditions and processing steps were similar to those employed in Example 2.

The results obtained are tabulated below.

First Maximum Density Neutralizing Solution added to First Developer Red Green Blue K Neutralizing Solution F 3.41 2.84 3.02 L Neutralizing Solution G 3.48 2.90 3.04 M Neutralizing Solution .l 3.27 2.61 2.72

When the neutralizing solution containing hydrazine was added to the first developer, a considerable lowering of the maximum density was found, but, on the contrary, substantially no lowering of the maximum density in the case of using the neutralizing solution containing sulfamic acid according to the invention was found.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. In a method for the development of an exposed silver halide photographic material including a prehardening treatment with an aldehyde hardener prior to developing, the improvement which comprises treating said silver halide photographic material between said prehardening and said developing with a bath containing a compound represented by the following general formula (I) R-NH 1.

in which R represents M, SO NH CH COOM or -C(CH OH and M represents an atom or group capable of imparting water solubility, or the following general formula (II) NH (II) R I in which R represents CH COOM or -CH CH OH and M has the same meaning as described above.

2. The method for development of claim I, wherein said compound represented by the general formula (I) or (II) is sulfamic acid, sulfarnide, glycine, tris(hydroxymethyl)aminomethane, iminodiacetic acid, or diethanolamine.

3. The method for development of claim 1, wherein said compound represented by the general formula (I) or (II) is glycine.

4. The method for development of claim 1, wherein said compound of the general fonnula (I) or (II) is present in said bath at a concentration of from 0.1 to 50 g per 1,000 ml of said bath.

5. The method for development of claim 1, wherein said bath has a neutral or acidic pH.

6. The method for development of claim 1, wherein said bath additionally contains at least one of a salt, a pH regulator, a buffering agent, an alkali halide, a fog inhibitor and a mildew preventing agent.

7. The method for development of claim 1, wherein said bath is at a temperature ranging from about 30C to about 60C.

Claims (7)

1. IN A METHOD FOR THE DEVELOPMENT OF AN EXPOSED SILVER HALIDE PHOTOGRAPHIC MATERIAL INCLUDING A PREHARDENING TREATMENT WITH AN ALDEHYDE HARDENER PRIOR TO DEVELOPING, THE IMPROVEMENT WHICH COMPRISES TREATING SAID SILVER HALIDE PHOTOGRAPHIC MATERIAL BETWEEN SAID PREHARDENING AND SAID DEVELOPING WITH A BATH CONTAINING A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA (I)

2. The method for development of claim 1, wherein said compound represented by the general formula (I) or (II) is sulfamic acid, sulfamide, glycine, tris(hydroxymethyl)aminomethane, iminodiacetic acid, or diethanolamine.

3. The method for development of claim 1, wherein said compound represented by the general formula (I) or (II) is glycine.

4. The method for development of claim 1, wherein said compound of the general formula (I) or (II) is present in said bath at a concentration of from 0.1 to 50 g per 1,000 ml of said bath.

5. The method for development of claim 1, wherein said bath has a neutral or acidic pH.

6. The method for development of claim 1, wherein said bath additionally contains at least one of a salt, a pH regulator, a buffering agent, an alkali halide, a fog inhibitor and a mildew preventing agent.

7. The method for development of claim 1, wherein said bath is at a temperature ranging from about 30*C to about 60*C.