JPS62231955A - Antiseptic agent of photographic colloid composition and its antisepticizing method - Google Patents

Abstract

PURPOSE:To preserve a photographic colloid composition against microorganisms and to enhance its preservativity by incorporating a specified compound as an antiseptic agent in the photographic colloid composition to be used for forming the constituent layer of a silver halide photographic sensitive material. CONSTITUTION:The photographic colloid composition to be used for forming the constituent layer of a silver halide photographic sensitive material contains as its antiseptic agent at least one of the compounds represented by formulae I-III in which R1 is alkylene; R2 is C2H4OH; R3 is 1-5C lower alkyl; and each of R1 and R3 has, preferably, 1 or 2C. The antiseptic agent containing as an effective component one of the compounds of formulae I-III is useful for preservation of the coating composition of a matting agent dispersion, a coupler dispersion, a silver halide emulsion, and an ultraviolet absorber dispersion, or a mixture of some of them.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to a preservative and a preservative method for a photographic colloid composition used in a silver halide photographic light-sensitive material (hereinafter simply referred to as "photosensitive material"). It is.

Prior art and its problems Photosensitive materials generally include at least one photosensitive emulsion layer and optionally a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, a backing layer, etc. It is formed by laminating constituent layers and coating them on a support.

These constituent layers may contain silver halide, silver halide, etc. in a hydrophilic binder such as gelatin, depending on the purpose of use of the photosensitive material.
Contains couplers, masking couplers, stabilizers, inhibitors, filter dyes, haleysilane inhibitor dyes, sensitizing dyes, colloidal silver, ultraviolet absorbers, antioxidants, matting agents, surfactants, etc.

These additives are usually dissolved or dispersed in an aqueous solvent such as water, alcohol, or a mixture thereof, or dissolved or dispersed in a high-boiling water-insoluble solvent or dispersed as minute oil droplets, and these additives are hydrophilic. It is added to a colloid to form a coating composition for constituent layers.

Hydrophilic colloids are polymeric substances used to prevent the aggregation of silver halide, colloidal silver, and other additives, with gelatin being the most widely used, and others such as albumin, agar, and gum arabic. natural substances such as acylated gelatin, fucurated gelatin, polymeric Mg2 bodies such as hydroxyethyl cellulose, polyvinyl alcohol, partially saponified polyvinyl acetate,
Water-soluble polymers such as polyacrylamide, poly-N, N-dimethylacrylamide, and polyvinylpyrrolidone are used.

However, the above-mentioned constituent layer additive solutions and constituent layer coating compositions are susceptible to the propagation of microorganisms such as bacteria and mold during storage, and when stored for a long period of time, they deteriorate or rot, resulting in a decrease in the viscosity of the coating composition. This results in a decrease in the physical strength of the surface film of the photosensitive material, and furthermore, the metabolites of the grown microorganisms adversely affect the photographic performance of the photosensitive material, resulting in serious defects.

In order to prevent the occurrence of defects caused by such microorganisms, it is known to add bactericides and fungicides to coating compositions.

In general, fungicides or antifungal agents include, for example, phenol, thymol, trichlorophenol, cresol, p.
-chloro-m-cresol, 0-phenylphenol,
Aromatic phenols such as chlorophyllan, 3,4.5-)ribromosalicylanilide, and 4-n-hexylresorcin; Compounds having a carbonyl group such as formaldehyde, paraformaldehyde, geltaraldehyde, and methylolchloraldehyde; Carboxylic acids or their esters such as benzoic acid, p-oxybenzoic acid ester, sorbic acid; Nitrogen-containing heterocyclic compounds such as 2-mercaptobenzothiazole and 2-(4-thiazolyl)benzimidazole; Phenylmercury, phenylpropionic acid water 111 mercury compounds; antibiotics such as neomycin and kanamycin; and others, some of which are also known to be used in photographic colloidal compositions.

However, conventional methods are not satisfactory because they are not effective unless added to the hydrophilic colloid in large quantities, are harmful to living organisms, or are harmful to photography.

For example, phenols cannot exhibit a sufficient preservative effect unless they are added in a large proportion of 2% or more of the hydrophilic colloid.

When formaldehyde or the like is used, the photosensitive material tends to be foggy.

Hengthiazoles and the like tend to have a degrading effect on the photosensitive material t4.

Mercury compounds are harmful to living organisms and their use must be avoided.

Furthermore, the benzisothiazolone described in JP-A No. 54-27424 tends to cause fogging of photosensitive materials, and the neomycin described in JP-A-42-14081 is expensive.

As described above, none of the conventional bactericides and antifouling agents have practically satisfactory properties when added to photographic colloid compositions as preservatives.

■Object of the Invention The first object of the present invention is to effectively protect additive solutions and coating compositions for constituent layers of photosensitive materials, that is, photographic colloid compositions, from microorganisms, and to improve their storage stability. Moreover, it is an object of the present invention to provide a preservative for a photographic colloid composition and a preservative method that can be used in a small amount.

A second object of the present invention is to provide a preservative for a photographic colloid composition and a method for preserving it, which does not adversely affect photographic performance such as sensitivity, fog, and preservability of light-sensitive materials.

Other objects of the invention will become apparent from the description below.

■Specific structure of the invention As a result of various studies, the present inventors have found that the compounds represented by the following general formulas 1 to 3 are all effective as preservatives for photographic colloid compositions. It has been found that the objects of the present invention can be achieved by incorporating at least one such compound into a photographic colloid composition.

General formula 1 % Formula % General formula 3 (However, R3 is an alkylene group, Rt is a C2H4OH group,
R1 represents a lower alkyl group having 1 to 5 carbon atoms.)
In the above general formula, Rt or R3 is particularly preferably one having 1 or 2 carbon atoms.

The preservative of the present invention containing the compounds represented by the above general formulas 1 to 3 as active ingredients is particularly suitable for use in cloak agent dispersions, coupler dispersions, silver halide emulsions, ultraviolet absorber dispersions, or mixtures thereof. It is particularly useful for preserving body coating compositions.

The amount of preservative used is from 0.001 to 0.001 to an aqueous solution of a photographic colloid composition and other solutions to which it should be added.
A range of 0.05% by weight is preferred. However, this range is
Of course, the amount may be increased or decreased depending on the type of photosensitive material, type of aqueous solution, storage conditions, etc.

The preservative of the present invention is water or methanol, ethanol,
It can be added as a solution dissolved in a solvent such as isopropanol, acetone, ethylene glycol, or a mixed solvent thereof (or it can be added by dissolving it in a high-boiling point solvent or a low-boiling point solvent and then emulsifying and dispersing it using a surfactant. It may also be added.

-IG Specific examples of compounds represented by formulas 1 to 3 are shown below.

Compound (1-1) Compound (2) JJH Compound (3-2) The timing of addition of the preservative of the present invention is arbitrarily selected depending on the time at which the preservative effect is expressed.

The photographic colloid composition to which the preservative of the present invention is added is a solution of a woody colloid in an aqueous solvent. The hydrophilic colloid and aqueous solvent used are as described above.

The additives contained in the photographic colloidal compositions of the present invention may be other than ordinary photographic additives, and particularly preferred examples thereof are shown below.

i) Coupler: α-(4-carboxyphenoxy)-α-pivalyl 2
-chloro-5-(γ-2.4-di-tert-amylphenoxy)butyramide]acetanilide, α-pivalyl-2-chloro-5-(γ-2.4-di-tert-amylphenoxy)butyramide]
ert-amylphenoxy)butyramide]acetanilide, α-benzoyl-2-chloro-5-(α-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide, α-(4-carboxyphenoxy)-α-bivalyl 2
-chloro5-(α-3-bentatecylphenoxy)butyramide]acetanilide, L-(2,4,6-)dichlorophenyl)-3-(3-(2,4-di-ter
t-amylphenoxyacetamide)penzamide)-
5-pyrazolone, 1-(2,4,6-dichlorophenyl)-3-(3-dodecylsuccinimidobenzamide) = 5-pyrazolone, 4.4°-methylenebis+ 1-(2,4,6-trichlorophenyl) )-3-(3-(2,4-tert
-amylphenoxyacetamide) henzamide]-
5-pyrazolone), 1-(2,4,6-)dichlorophenyl)-3-(2-
l Coro-5-octadecylsuccinimide anilino)-
5-pyrazolone, 1-(2,4,6-trichlorophenyl)-3-(2-
Chloro-5-tetradecanamidoanilino)-5-pyrazolone, l-hydroxy-N-(8-(2,4-di-tsrt-
amylphenoxy)butyl-2-naphthamide, 2,4-dichloro-3-butyl-6-(2,4-di
tert-amylphenoxyacetamide) phenol, 1-hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-(8-(2,4-di-tert-amylphenoxy)butyl-2-naphthamide, etc.).

ii) High boiling point solvent dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phthalate, N, N
-diethyldodecaneamide, di-natoxyethyl phthalate, and others.

iii) Noble metal sensitizers: chloroauric acid, potassium chlorooleite, potassium aurithiocyanate, ammonium chlorovaladate, sodium chlorovaradate, and others.

iv) Sulfur sensitizer; active gelatin, sodium thiosulfate, ammonium thiosulfate, N-allylrhodanine, etc.

V) Reduction sensitizer; stannous chloride, tetraethylenetriamine, iminoaminomethanesulfinic acid, and others.

vi) Sensitizing dye; anhydro-9-ethyl-bis(3-sulfopropyl-
5-chloro)oxacarbocyanine hydroxide, anhydro-9-ethyl-bis(3-sulfobutyl-5
-chloro)thiacarbocyanine hydroxide, 3-sulfobutyl-3°-ethylthiacyanine sodium salt, and others.

vi) Stabilizer: 4-hydroxy-6-methyl-1,3,3a,? -Tetrazaindene, benzothiazole, and others.

vi) Matting agents Nisilica, magnesium phosphate, titanium oxide, polymethyl methacrylate, polystyrene, starch, cellulose acetate propionate, and others.

ix) Surfactant: saponin, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether,
Polyoxyethylene-bolyglycidal block copolymer, etc.

X) Polymer hydrophilic colloid: Copolymers of methyl methacrylate, n-butyl acrylate, butadiene, styrene, vinyl acetate, vinyl chloride, etc.

As the silver halide, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. may be used.

■Specific effects of the invention According to the present invention, a preservative containing one or more of the compounds represented by the above general formulas 1 to 3 as an active ingredient is added to a photographic colloid composition used for coating photosensitive materials. Since the agent is added,
Due to the preservative action of the compound, the photographic colloid composition can be effectively protected from microorganisms, and excellent storage stability can be obtained.

Moreover, the amount of the preservative used is sufficient.

Moreover, it does not have any adverse effect on the photographic performance of the light-sensitive material, such as sensitivity, fog, and storage stability.

Furthermore, since the preservative is inexpensive, it does not increase the cost of photosensitive materials unlike antibiotics.

Therefore, the burden on equipment such as storage equipment, constraints on production planning, failures in photographic performance and physical properties, etc. can be significantly alleviated.
This can bring about significant effects such as improved productivity of photosensitive materials and improved quality reliability.

(2) Specific Examples of the Invention The present invention will be explained in more detail below with reference to specific examples.

Example 1 Compound (1-1), compound (2) and compound (3) according to the present invention as preservatives were added to an aqueous dispersion 11 of a mantle agent made of polymethyl methacrylate having an average particle size of 3.
A total of three types of matting agent dispersions were prepared by adding 25 μm of each of -1). These are designated as samples 1 to 3.

A total of two types of comparative matting agent dispersions were prepared in the same manner except that phenol and benzisothiazolone were used as comparative preservatives and 25 μm of each was added.

These will be referred to as Comparative Sample 1 and Comparative Sample 2.

Furthermore, Pseu
Inoculated with one strain of the genus Don+onas and incubated at a temperature of 25°C.
A storage test was conducted in which the matting agent was left for a week, and the number of bacteria was measured after the storage period had elapsed, and the dispersion state of the matting agent was also observed. Further, a matting agent dispersion without adding preservatives was used as a control, and the case where this was used as it was without storage was referred to as Control Sample 1, and the case where a similar storage test was conducted was referred to as Control Sample 2. The results are shown in Table 1.

Further, a highly sensitive X-ray photosensitive material was produced using the above-mentioned seven types of matting agent dispersions in total by the following method.

That is, 2.5 potassium iodide is added to the gelatin aqueous solution.
A potassium bromide solution containing mol % and an ammoniacal silver nitrate solution were added by a double jet method while gradually increasing the flow rate to obtain a silver iodobromide regular octahedral monodisperse emulsion having an average grain size of 1.05 JllI+. Further, an ammoniacal silver nitrate solution and a potassium bromide solution were added by a double jet method to form a shell of pure silver bromide. During this time, pAg was maintained at 10.0, and pH was gradually lowered from 9.0 to 8.0. This emulsion was a regular octahedral monodispersed emulsion with an average grain size of 1.25 nm.

After desalting, this emulsion was subjected to gold sensitization and sulfur aggravation treatment, and then 4-hydroxy-6-methyl-1,3,3a
, ? - Tetrazaindene was added to stabilize the mixture, and common photographic additives such as a spreading agent and a hardening agent were added to obtain a highly sensitive X-ray silver iodobromide emulsion.

On the other hand, a coating solution for a protective layer having the following composition was prepared using each of the seven types of mantle agent dispersions described above.

Gelatin 50g Sodium diisooctylsulfosuccinate (1% aqueous solution) 30ml Antistatic agent 2g Matting agent dispersion
30 g water The entire surface becomes IE.The above high-sensitivity Silver amount is 30a+g/100cj
A highly sensitive X-ray photosensitive material was produced.

These X! ,? ! Sensitometry was performed using each of the photosensitive materials as a sample according to the following conditions.

For exposure, the sample is placed on one side of the transparent support using two optical urchins.
The film was held between two plates and exposed for 1/10 seconds from both sides at the same time using a light source with a color temperature of 5,400 @. This was done using a developing machine.

Nee mutual 11JflLL processing single plate development 3
Constant at 5℃ for 25 seconds i Wash with water at 34℃ for 25 seconds Dry at 33℃ for 25 seconds 45℃ for 15 seconds The developer used here has the following composition, and the fixer is acidic hardening fixer "Sakushi XFJ ( I used Roku Konishi Photo Industry!!

[Developer composition]

Potassium VAite 55.0 g
Hydroquinone 25.0 g
-Phenyl-3-pyrazolidone 1.2g boric acid
10.0 g potassium hydroxide 21.0 g triethylene glycol 17.5 g 5-methylbenztriazole 0.04 g 5-nitropenzimidazole 0.11 gl-phenyl-5-mercaptotetrazole 0.015 g glacial acetic acid 16.0 g Potassium bromide 4.0g water
Table 1 shows the quantity results that total 11.
Sensitivity was expressed as relative sensitivity, with the sensitivity of control sample 1 being 100.

From the results in Table 1, it can be seen that in Sample 1, Sample 2, and Sample 3 according to the present invention, there was no adverse effect on photographic performance, and bacterial activity was effectively suppressed. It is also clear that no aggregation of the matting agent occurred.

Example 2 A color ultraviolet absorber dispersion was prepared using an ultraviolet absorber represented by the following structural formula.

Further, a green-sensitive silver iodobromide emulsion for a high-speed layer was obtained using tetradecahedral silver iodobromide having an average grain size of 1% and containing 4 mol% of silver iodide.

For each of the above-mentioned color ultraviolet absorber dispersion and green-sensitive silver iodobromide emulsion, 10 μ of the compound (1-1) described above according to the present invention was added as a preservative, and the compound (
2) was added at a ratio of 25 .mu., compound (3-1) at 10 .mu., and phenol as a comparative compound at a ratio of 25 .mu. These are referred to as Samples 4 to 6 and Comparative Sample 3.

And Pseudomonas in the ultraviolet absorber dispersion
A green-sensitive silver iodobromide emulsion was inoculated with one strain of A.
One strain of c1netobacter genus was inoculated and the temperature was 2.
A storage test was performed by leaving the samples at 5°C for one week, and the number of bacteria was measured. In addition, a sample without preservatives was used as a control, and the case where it was used as it was without storage was called Control Sample 3, and the case where the same preservation test was performed was Control Sample 4.
shall be. The results are shown in Table 2.

In addition, the following layers 1-
A highly sensitive multilayer color negative bad light material constituted by layer 10 was produced. That is, the above-mentioned ultraviolet absorber dispersion was used to form the protective layer of layer 10, and the above-mentioned green-sensitive silver iodobromide emulsion was used to form the high-sensitivity green-sensitive emulsion layer of layer 6. Furthermore, the average particle size is 4p! Type 111 iodobromide containing 5 mole percent silver iodide in n was used as the green-sensitive iodobromide primate in layer 5, a low-speed green-sensitive emulsion layer.

In the following, the amounts added to the silver halide color photographic light-sensitive material are shown as values per 1 m1, and the amounts of silver halide emulsion and colloidal silver are shown as values converted to silver.

Layer 1: Halley silane prevention layer containing 1!0.4 g of black colloid and 3 g of gelatin.

A layer of 11.4 g of low-speed red-sensitive silver iodobromide emulsion (Ag16
mol %), 1.2 g gelatin and 0.8 g cyan coupler (C-1), 0.065 g colored cyan coupler (CC-1) and 0.015 g DIR
A low-speed red-sensitive emulsion layer containing 0.65 g of tricrendyl phosphate in which compound (D-1) was dissolved.

Layer 3: Contains 1.3 g of emulsion (Ag 15 mol %) color-sensitized to red window light, and contains 1.2 g of gelatin and 0.21 g of cyan coupler (C-1); ．．
A highly sensitive red-sensitive emulsion containing 0.23 g of dibutyl phthalate dissolved in 0.2 g of colored cyan coupler (CC-1).

N4: 0.01 g of 2.5-di-tar t-octylhydroquinone (hereinafter referred to as "stain inhibitor (IIQ-1)" J
An intermediate layer containing 0.04 g of di-n-butyl phthalate and 0.8 g of gelatin dissolved therein.

1i5: 1.4 g of the above low-sensitivity green-sensitive silver iodobromide emulsion (
Ag1 5 mol%), 262 g of gelatin and 0.8
g of magenta coupler, 0.15 g of colored magenta coupler (CM-1) and 0.016 g of l1l
A low-speed green-sensitive emulsion layer containing 0.67 g of tricresyl phosphate in which l+ compound (D-1) was dissolved.

Layer 6: Contains 1.3 g of emulsion (Agl 4 mol %) of the above-mentioned high-speed-like malignant silver iodobromide emulsion color-sensitized to green sensitivity, 1.2 g of gelatin, and 0.2 g of gelatin. A highly sensitive green-sensitive emulsion layer containing magenta coupler (M-1) and 0.22 g of dibutyl phthalate in which 0.02 g of colored magenta coupler (CM-1) was dissolved.

Layer 7: One layer of yellow filter containing 0.15 g of yellow slurry, 11 g of dibutyl phthalate dissolved in 0.2 g of antifouling agent (HQ-1) and 1.5 g of gelatin.

Layer 8: 0.5g of low-speed blue-sensitive silver iodobromide emulsion (Ag1
6 mol %), 1.9 g of gelatin and 1.5 g of yellow coupler (Y-1) in a low-speed blue-sensitive emulsion layer containing 0.6 g of dibutyl phthalate.

Layer 9:1. Contains a blue-sensitive emulsion obtained by chemically ripening an emulsion of Og (Ag1 5 mol %), 1.5 g of gelatin and 1.5 g of gelatin.
．． 0,6 in which 3g of yellow coupler (Y-1) was dissolved
High speed blue sensitive emulsion layer containing 5 g of tricresyl phosphate.

Layer IO: protective layer containing the UV absorber dispersion described above and polymethyl methacrylate as cloaking agent and 2.3 g of gelatin.

(C-1) CsH++ (CC-1) (M-1) (CM-1) I I (D-1) (Y-1) I After performing wedge exposure on the obtained photosensitive material through a green filter , Development processing was performed according to the following conditions, and sensitometry was performed.

Furthermore, the obtained photosensitive material was heated at a temperature of 25°C and a relative humidity of 60%.
Sensitometry was performed in the same manner on samples stored for three months in an atmosphere of

[Development process]

Color development at 38°C for 3 minutes and 15 seconds Bleaching at 38°C for 6 minutes and 30 seconds Washing with water at 38°C for 3 minutes and 15 seconds Fixing at 38°C for 6 minutes and 30 seconds Washing with water at 38°C for 3 minutes and 15 seconds Stable bath: 38° C., 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine A sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Odor Sodium chloride 1.3g Nitrilotriacetic acid trisodium salt monohydrate 2.5g Potassium hydroxide 1.0g or more of the ingredients were added with water to make 11, and the pH was adjusted to 10.0.

[Bleach i composition]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water was added to bring the concentration to 11, and the pH was adjusted to 6.0.

[Fixer composition]

Ammonium thiosulfate 50% aqueous solution 162 ml
Anhydrous sodium sulfite 12.4 g or more of the ingredients were added with water to make a total of 11, and the pH was adjusted to 6.5.

[Stable bath composition]

Formalin 37% aqueous solution 5.0 m
l Conidax (manufactured by Konishiroku Photo Industry) 7.5
Water is added to the components with SO1 or higher to make 11.

The results are shown in Table 2. The sensitivity is 10 times the sensitivity of control sample 3.
The relative sensitivity is expressed as 0.

From the results in Table 2, it can be seen that in the case of Samples 4, 5, and 6 according to the present invention, there is no adverse effect on the photographic performance of the resulting light-sensitive materials, and a strong inhibitory effect on bacterial growth is obtained. is clear. On the other hand, in the control sample in which no preservative was added or in the comparative sample 3 in which phenol was used as a preservative, the sensitivity of the obtained photosensitive material decreased due to decay due to bacteria.
An increase in Dmin was observed.

Claims (1)

[Scope of Claims] 1) A preservative for a photographic colloid composition, which contains at least one compound represented by the following general formulas 1 to 3 as an active ingredient. General formula 1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula 2 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula 3 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 is an alkylene group, R_2 is C_2H_2
The OH group and R_3 represent a lower alkyl group having 1 to 5 carbon atoms. 2) A photograph characterized in that a photographic colloid composition used for coating the constituent layers of a silver halide photographic light-sensitive material contains at least one compound represented by the following general formulas 1 to 3. A method for preserving colloidal compositions for use. General formula 1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula 2 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula 3 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 is an alkylene group, R_2 is C_2H_4
The OH group and R_3 represent a lower alkyl group having 1 to 5 carbon atoms. )