JPH0362027A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having superior resistance to formaldehyde by forming at least one photographic constituent layer contg. a compd. having a formaldehyde scavenger moiety and a water soluble polymer moiety. CONSTITUTION:At least one photographic constituent layer contg. a compd. having a formaldehyde scavenger moiety and a water soluble polymer moiety is formed. The compd. is a water soluble high molecular compd. modified with a formaldehyde scavenger and the water soluble polymer is preferably a polymer having many hydrophilic groups such as hydroxyl and carboxyl groups, especially gelatin. The constituent compd. of the formaldehyde scavenger moiety is a compd. forming a substance harmless to photographic performance by a reaction with aldehyde compds. such as formaldehyde. A sensitive material hardly deteriorating physical properties as a film in spite of satisfactory resistance to formaldehyde can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material having excellent resistance to formalin gas. The present invention can be particularly suitably used as a silver halide color photographic light-sensitive material having excellent resistance to formalin gas.

[Conventional technology]

It is well known that the performance of silver halide photographic materials is affected by the effects of various harmful gases.

Among them, formalin (formaldehyde) is a resin raw material, bactericidal agent, and hardening agent.

It is used as an adhesive for furniture, building materials, clothing, etc. When silver halide photographic materials, especially silver halide color photographic materials, are stored for a long period of time in such an environment, couplers and other substances may Various constituent compounds react with formalin, causing undesirable changes such as a decrease in color density, staining, and an increase in fog density.

In order to prevent such deterioration of photographic performance, a technique has been developed in which a photosensitive material contains a compound (formalin scavenger) that reacts with formalin and converts it into a harmless substance.

Examples of such techniques are Japanese Patent Publications No. 46-34675, No. 4B-38418, No. 51-23908, and Japanese Patent Publication No. 51-23908.
No. 0-87023, No. 57-133450, No. 58-
No. 150950, No. 5B-79248, U.S. Patent No. 2
．． No. 895.827, No. 3,652,278, No. 3770.431, No. 3,811.891, No. 4,0
No. 03,748, No. 4,411,987, No. 4,14
4.309, 4,418.142, 4,464
, 463, US Defense Patent No. 900.028, West German Patent No. 3,223,699, West German Patent No. 3,227,961,
3゜227, No. 962, Research Disclosure No. 10.133, etc.

However, these compounds have the disadvantage of deteriorating film properties such as brittleness and hardness when added to photosensitive materials in sufficient amounts to obtain sufficient effects. is known to be a pyrazolone-based 4-equivalent magenta coupler, and it is clear that it is preferable to contain a large amount in the layer containing the magenta coupler and/or the layer above it, but these formalin scavengers All of them have the problem that they are highly water-soluble and diffuse uniformly into the photosensitive material, so that they do not function effectively.

If a new oily group (ballast group) is introduced into these formalin scavengers and added by oil-protect dispersion, diffusion in the photosensitive material can be suppressed, but this will weaken the formalin scavenging effect.

Further, due to problems with the film properties, it is not possible to add a large amount, and in the end it is not possible to use an amount that will provide a sufficient effect.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a photosensitive material in which the degree of deterioration of film properties is small despite having sufficient formalin resistance, and in which a formalin scavenger is effectively incorporated into a desired layer. The purpose of the present invention is to provide a silver oxide photographic material.

[Structure of the invention]

The above object of the present invention is to provide a silver halide film characterized by having at least one photographic constituent layer containing a compound having a formalin scavenger moiety and a water-soluble polymer moiety (hereinafter also referred to as "compound of the present invention"). This was achieved using photographic materials.

The present invention will be explained in more detail below.

The compound of the present invention is a water-soluble polymer compound modified with a formalin scavenger.

The water-soluble polymer constituting the compound of the present invention preferably has many hydrophilic groups such as hydroxyl groups, amino groups, and carboxyl groups. The term "aqueous solution" here includes a solution that contains water and becomes a gel.

Examples of water-soluble polymers include natural polymer compounds such as gelatin, albumin, and starch, polyvinyl alcohol,
Synthetic polymer compounds such as polyacrylamide and polyacrylic acid can be mentioned.

Among these, gelatin is particularly preferred.

The compound constituting the formalin scavenger portion of the compound of the present invention is a compound that reacts with an aldehyde compound such as formalin gas to produce a substance that is harmless in terms of photographic performance, preferably a substantially colorless compound. Examples thereof include the compounds described in the above-mentioned patents relating to formalin scavengers, and derivatives thereof, and those represented by the following general formula (S) are particularly preferred.

General formula [S] R' -A -R'' Here, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a carbamoyl group, an iminomethyl group, or an amino group, and includes those having a substituent, including those in which R1 and R2 form a ring, and when R1 and R2 do not form a ring, at least one of these R1 and R2 is an acyl group, a carbamoyl group, or a general formula Among the formalin scavengers represented by (S), preferred are general formulas (S-I), (S
-If), (S-I[1:l or (S-IV)).

General formula (S-1) ○ 1 (H, N-C-NHS TR3 general formula [S ■〕 general formula %formula%) general formula (S-rV) 11 here, Rco represents a divalent alkyl group, 4 5 and R? is a hydrogen atom, alkenyl group, Archi group or -C-R' 1 (R' is an alkyl group.

), R6 represents a hydrogen atom, an alkyl group or an amino group, R9 represents an alkyl group, and the polygroup includes those having a substituent. Furthermore, R4 and R6 and R7 and R9 include those forming a ring. The substituent includes an amino group, a hydrocarbon residue, or an OR' group (R' is a hydrocarbon residue)
can be mentioned. R8 is a carbonyl group, -〇 (=NH)
- group, RIG represents a hydrogen atom, an alkyl group, a cyclohexyl group, a phenyl group, an aralkyl group, an alkoxyl group, an aryloxyl group, a carbamoyl group, an alkoxycarbonyl group, and a cyano group, and these polygroups have a substituent. Including those who have. R" represents a hydrogen atom, an alkyl group, a cyclohexyl group, a phenyl group, an aralkyl group, a heterocyclic residue, a benzoyl group, a sulfone alkyl group, a sulfone aryl group, a carboxyalkyl group, a carbamoyl group, a thiocarbamoyl group, and includes those having substituents.

The compound of the present invention has a formalin scavenger moiety and a water-soluble polymer moiety, but the metal compound of the present invention includes:
Examples include those in which both parts are bonded through various bonds such as amide, sulfonamide, ureido, thioureido, ester, and urethane.

Preferred formalin scavenger moieties in the compounds of the present invention are illustrated below. 6 or less margin (1) HzNCNHCHzCHNHCNHz C〇- 0 CIl□NH し11zLI - CH,C0 CH2NI+ CH,C0 H20 11 CH2C0 C)12NH ~11 υ 0 CH,0 H (60) The present invention The method for producing the compound, i.e. The water-soluble polymer and the formalin scavenger may be bound by any method as long as it does not significantly impair the properties of the formalin scavenger.

For specific bonding methods, see "Chemical Modification of Collagen and Gelatin," Harukazu Toyoda and Yasumasa Chonan: Leather Chemistry, 30 (
1), 3 (1984), but
Representative methods are listed below.

1) Agono group bonded to the main chain or side chain of the water-soluble polymer (if the water-soluble polymer is gelatin, the α-amino group of the polypeptide chain of gelatin), the α-amino group of the terminal amino acid, or lysine carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, chloroformyl group, chlorosulfonyl group, isocyanate group, isothiocyanate group, chloro A method of reacting carbonyloxy groups to form amide bonds, sulfonamide bonds, ureido bonds, thiouraid bonds, and urethane bonds.

2) Carboxyl group bonded to the main chain or side chain of the water-soluble polymer (when the water-soluble polymer is gelatin, the α- of the carboxyl terminal amino acid of the polypeptide chain of gelatin)
After activating the carboxyl group (β-carboxyl group on the side chain of an aspartic acid residue or γ-carboxyl group on the side chain of a glutamic acid residue) with water-soluble carbodiimide, the carboxyl group was bound to a formalin scavenger. A method of reacting an a[no group or a hydroxyl group to form an a5do bond or an ester bond.

3) A method in which a carboxyl group bonded to a formalin scavenger is activated and reacted with a diroxy group bonded to the main chain or side chain of a water-soluble polymer to form an ester bond.

4) The amino group, carboxyl group, or hydroxyl group bonded to the chain or side chain of the water-soluble polymer and the amino group, carboxyl group, or hydroxyl group bonded to the formalin scavenger are
, (a method of linking by a compound having two reactive groups represented by t.

Xl and X2 are carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, chloroformyl group,
Chlorosulfonyl group, isocyanate group, isothiocyanate group, chlorocarbonyloxy group, arylcarbonyloxy group, hydroxy group, amino group, fluorine atom,
Represents a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonyloxy group, and an alkylsulfonyloxy group, and L■
represents a divalent linking group such as a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heterocyclic group.

As a method for activating carboxyl groups, N, N'
-dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), 1-cyclohexyl-3-(2-morpholinyl-4-ethyl>carbodiimide meth-p-
) Luenesulfonate (CMC), 1-benzyl-3
-(3-dimethylaminopropyl)carbodiimide (B
water-soluble carbodiimide such as DC), N-ethyl-5=
Method using condensation reagents such as phenyl isoxazolium-3'-sulfonate (Woodward reagent K), pentachlorophenyl chloroacetate) (TCA-OPCP)
, p-nitrophenyl trifluoroacetate (TF
A-OPNP), an active ester method using p-nitrophenyl chloroformate, etc., an acid chloride method using thionyl chloride, etc.

Examples of the compounds of the present invention are shown below, but other compounds can be synthesized in the same manner.

Combination Example-1〉 500μ of allantoin-4-carboxylic acid in 200mZ of water
The pH was adjusted to 4.5.

Next, 1-ethyl-3-(3-dimethylaminopropyl)
- 500 μl of carbodiimide hydrochloride was added and the reaction was allowed to proceed for 30 minutes while maintaining the pH at 4.7.

Thereafter, 150 ml of 5% gelatin solution (solution dissolved in 0.1 molar phosphate buffer, pH 8.0) was added, and the mixture was stirred at 40°C for 2 hours. After the reaction, dialysis, ultrafiltration, concentration, and lyophilization were performed to obtain 6.0 g of the target product.

The introduction rate of allantoin-4-carboxylic acid is 1.3wt
! Met.

Synthesis Example-2> 450 μm of 4-carboxyphthalimide was dissolved in 200 μm of water, and the pH was adjusted to 4.5.

Then 1-ethyl-3-(3-dimethylacunopropyl)
- 500 μl of carbodiimide hydrochloride was added and the reaction was allowed to proceed for 30 minutes while maintaining the pH at 4.7.

Thereafter, in exactly the same manner as in Synthesis Example 1, 5.9 g of the target product was obtained.

The introduction rate of 4-carboxyphthalimide is 1.3wt2
Met.

Synthesis Example-3> 5 g of 4-aminomethylhydantoin in 2000 ml of water
The pH was adjusted to 4.5.

Then l-ethyl-3-(3-dimethylaminopropyl)
- 5 g of carbodiimide hydrochloride was added and reacted for 30 minutes while maintaining the pH at 4.7.

Thereafter, a solution prepared by dissolving 10 g of polyacrylic acid in 0.1 molar phosphate buffer (pH 8,0) 150- was added, followed by stirring at 40°C for 2 hours.

After the reaction, the reaction mixture was subjected to dialysis, ultrafiltration, concentration, and lyophilization to obtain 12.0 g of the target product. The introduction rate of 4-aminomethylhydantoin was 25% and 1t%.

The compound of the present invention can be contained in any layer of a light-sensitive material, for example, when used in a silver halide color photographic light-sensitive material, its protective layer, silver halide emulsion layer, intermediate layer, filter layer, antihalation layer, It can be used by being included in at least one of the other layers. Preferably, it is a layer farther from the support than the silver halide emulsion layer and/or nucleus layer containing the magenta coupler, and it is better to contain it in a layer where no dye is formed than in a layer in which a dye is formed by development.

The amount of the compound of the present invention added is such that the formalin scavenger portion is 5×10 per m2 of the silver halide photographic light-sensitive material.
-' mol to 1 mol is suitable and preferred, more preferably lXl0-'mol-5X10-', even more preferably lXl0-'mol-5X10-' The silver halide photographic light-sensitive material of the present invention is as follows. It can be applied to various types of photosensitive materials.

For example, for general black and white, for X-ray recording, for plate making, for color positive, for color negative, for color paper, for reverse color,
U.S. Pat. No. 2,996.382 and U.S. Pat. No. 3,178,282 using photosensitive materials for direct positive use, heat development use, etc., or surface latent image type silver halide grains and silver halide grains having internal fog nuclei. It can be used in photosensitive materials produced by the method described in the specification of the present invention.

It is particularly advantageous to apply the method to color photosensitive materials having a multilayer structure.

In the present invention, the silver halide emulsion includes any silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

The halide root grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Dispersed emulsions may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Anticapri agents, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

When producing a color light-sensitive material, a coupler is generally used in the emulsion layer. Competing couplers that have a color correction effect, and campling with oxidized developing agents can produce development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, and capping agents. Compounds that release photographically useful fragments can be used, such as antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, an ultraviolet absorber, a fluorescent whitening agent, a surfactant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

Any means can be used to develop the photosensitive material of the present invention, such as known methods. The processing temperature is preferably between 18°C and 50°C, and depending on the purpose, any of black and white photographic processing, lithographic development processing, or color photographic processing to form a dye image can be applied. In addition, in photosensitive materials for heat development, preferably 100
Processed at temperatures above ℃.

Margin 1 below: [Example] The present invention will be explained in more detail with reference to Examples below.
This is an example for explaining the present invention, and the present invention is not limited thereto.

Prior to specific explanation of each example, the production of silver halide emulsions used in the examples will be explained.

A gelatin aqueous solution was put into a reaction pot, and the p in the reaction pot was
While controlling Ag and pH, silver nitrate aqueous solution,
After adding an aqueous potassium iodide solution and an aqueous potassium bromide solution simultaneously while controlling the addition time, precipitation and desalination were performed using pH-coagulating gelatin, and gelatin was added to form seed emulsion N.
E-1 was prepared.

The average grain size of seed emulsion NE-1 was 0.093 μm.

Put the above seed emulsion and gelatin aqueous solution into a reaction pot.
While controlling the pAg and pH in the reaction vessel, add ammoniacal silver nitrate aqueous solution, potassium iodide aqueous solution, and potassium bromide aqueous solution in proportion to the surface area during particle lengthening, and add potassium bromide at an appropriate particle size. The solution was changed to a solution and continued addition was made. In the same way as the seed emulsion, precipitate and desalt, add gelatin and redisperse to give a pAg of 7.8 and a pH of 6.
, 0 emulsion was obtained.

In this way, silver iodobromide emulsion E with an extremely high content inside the grains
M-1 to EM-2 were prepared.

Table 1 shows each emulsion and its contents.

Next, examples will be explained in detail.

Example 1 Multilayer color photosensitive material sample 11!l having a multilayer structure having the following composition on a subbed cellulose acetate support of 11hlO1('')
101 was created.

Coating amounts are expressed in g/m2 in terms of silver for silver halides and colloidal silver, and in g/m'' for additives and gelatin. The dyes, couplers, and DIR compounds are expressed in moles per mole of silver halide in the same layer.The emulsion contained in each color-sensitive emulsion layer was optimally enhanced with sodium thiosulfate and chloroauric acid. I gave it a feeling.

Margin sensitizing dye l Sensitizing dye V -1 M -1 8 +114 C-1 V UV-2 C-3 5-1 1'1M (D-1) (D-3) ■ Below, each layer of the above composition HC, ILl, R-
1, R-2, IL-2, G-1, G-2, YC, B
1. They shall be indicated by the abbreviations B-2, Pro-1, and Pro-2.

In addition to the above components, a surfactant was added to each layer as a coating aid.

Uhiro 102-106 = 1 G 1. G-2, YC, B-1, B-2, Pr.

1. Comparative formalin scanner FS to Pro-2
-1 to FS-5 were added. Other than that, sample 11h10
Sample seeds 102 to 106 were produced in the same manner as in Example 1.

Addition amount is 5 x 10 per 1m'' by adding up the addition amount of each layer.
-3 moles. The types of formalin scavengers used for comparison are as shown in the "Compound" column of Table 3.

Margins below S-1 S-2 S-4 S S-5 Magnetic 107-113(') Sample NLIL101 G-1, G-2, YC, B-1゜B-2, Pro-1, Pro- 1 t of sample except that 40% of the gelatin contained in No. 2 was replaced with the compound of the present invention.
It was produced in the same manner as lo1.

The types of compounds of the present invention are as shown in Table-2.

G-1, G-2, YC, B-1゜B-2 of Sample Hiro 101 on floors 114-122 ()
, 15% of gelatin contained in Pro-1, Pro-2
Sample M101 was prepared in the same manner as sample M101, except that the sample M101 was replaced with the compound of the present invention.

The types of compounds of the present invention are as shown in Table-2.

Each sample was cut and the maximum concentration deterioration under formalin gas atmosphere was evaluated.

Each sample was subjected to Treatment-2 as a formalin treatment and Treatment-1 as a reference treatment.

Treatment-1 A liquid containing 300 cc of 35% glycerin aqueous solution was placed at the bottom, and the sample was held at 30° C. for 3 days in a closed container filled with air equilibrated with this.

Treatment-2 A solution containing 6 cc of 40% formaldehyde aqueous solution per 300 cc of 35% glycerin aqueous solution was placed at the bottom, and a sealed container filled with air equilibrated with this was placed at 30°C for 3
Retain samples for days.

Thereafter, wedge exposure was performed according to a conventional method, and the following development treatment was performed.

Margin below Treatment process (38℃) Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Fixed arrival time: 6 minutes 30 seconds Water Wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds drying The composition of the treatment liquid used in each treatment step is shown below.

Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate
4.75 g anhydrous sodium sulfite
4.25g5g Hydroxylaminate 2.0
g Anhydrous potassium carbonate 37.5 g Potassium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 11. (pH=10.02) Bleaching solution> Iron (III) ethylenediaminetetraacetic acid Ammonium salt 100.0 g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water Add it to 12 and adjust the pH to 6.0 using ammonia water.
Adjust to.

Fixer> Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Add water and 11
and adjust the pH to 6.0 using acetic acid.

Stabilizing liquid> Formalin (37% aqueous solution) 1.5 m
Z Konidax (manufactured by Konica Corporation) 1.5r
d Add water to make 11.

In this way, changes in performance of the sample (reference) subjected to Process 1 (treatment without contact with formalin gas) and the sample subjected to Process 2 (treatment in contact with formalin gas) were evaluated based on the image survival rate.

The results for the green photosensitive layer are shown in Table 3.

As the residual rate, the percentage of the maximum concentration of the sample subjected to treatment-2 relative to the maximum concentration of the sample subjected to treatment-1 was used.

That is, the larger the value, the better the resistance to formalin gas.

In addition, the fragility of each sample was evaluated by the following method.

Cut each sample into a size of 3.5cm x 3Qcm,
After conditioning the humidity for 3 days at a relative concentration of 20% °C, it was evaluated by the method using a wedge-shaped tester described in Photographic Inc. Science and Engineering, Vol. 1, page 63 (1957). Note that this test is indicated by the length at break (am), and the longer the length at break, the poorer the brittleness.

Below is the margin table Table G selling> In the table, sample 11h107. The gelatin in ILL 112 has an amino group attached to a scavenger moiety, and Th
Gelatin at 108-110°113 has a carboxyl group bonded to a scavenger moiety, and NIIL114-
Polyvinyl alcohol in 119 has hydroxyl l
! In the polyacrylic acid in JJ<, N[L120-122, the carboxyl group is bonded to a portion of the scavenger.

As is clear from Table 3, when formalin scavengers other than those of the present invention are added, although there is an effect on the residual rate, the brittleness deteriorates.

On the other hand, when the compound of the present invention was used, a good survival rate was exhibited without deteriorating the brittleness.

Moreover, when the present invention is used, the same effect can be obtained even when the amount of formalin scavenger added is small.

〔Effect of the invention〕

As described above, according to the present invention, the image retention rate is good, the influence of formalin can be effectively removed, and there is no need to use an amount that would adversely affect the physical properties of the film, but rather this effect can be achieved with a small amount. achievable and prevent deterioration of vulnerability. Since the compound of the present invention can be effectively incorporated into a necessary layer, it is considered that this effect is fully exhibited.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a compound having a formalin scavenger portion and a water-soluble polymer portion.