JPH0553236A - Method for hardening gelatin - Google Patents

Abstract

PURPOSE:To accelerate hardening action and to prevent harmful action on the properties of a photographic material by using a specified compd. as a gelatin hardening agent. CONSTITUTION:A compd. represented by the formula is used as a gelatin hardening agent. In the formula, A is O or S, each of R<1> and R<2> is H, optionally substd. alkyl, aryl or aralkyl, R<1> and R<2> may form a ring through C, N, S, O, -C(=O)-, -SO2-, -C(=S)-, etc., and in the case where N is contained, -CH2 SO2CH=CH2 may be substd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hardening gelatin with an improved hardener, and more particularly to a method for hardening gelatin used in a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Layered gelatin is used as a binder in many photographic light-sensitive materials. In order to enhance the water resistance and mechanical strength of the gelatin layer, a method of hardening gelatin using various compounds has been conventionally known.

Aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 3,28
Compounds having a reactive halogen described in US Pat. No. 8,775, etc., aziridine compounds described in US Pat. No. 3,017,280, US Pat. No. 3,091,537, etc. Known epoxy compounds, halogen carboxyl aldehydes such as mucochloric acid, dioxane such as dihydroxydioxane and dichlorodioxane, and chromium alum, zirconium sulfate and the like are known as inorganic hardeners.

However, when these known gelatin hardeners are used in photographic light-sensitive materials, the hardening action is not sufficient, and the hardening degree referred to as "post-hardening", which is caused by a slow hardening reaction to gelatin, changes over time. There are many things.

As means for solving this problem, US Pat. No. 3,642,486, JP-B-47-8736, JP-B-49-13563, JP-A-53-41221, JP-A-53-57257, JP-B-58-32699,
JP-A-60-225148, JP-A-61-19641
And Japanese Patent Laid-Open No. 2-2114040. These curing agents have the characteristic that the curing action is fast and therefore the amount of post-hardening is small. However, these curing agents sometimes adversely affect the properties of the photographic light-sensitive material (for example, deterioration of adhesion resistance, increase of fog, decrease of photosensitivity, etc.) and the commercial value thereof is extremely deteriorated.

[0006]

The first object of the present invention is to provide a method for hardening gelatin with a novel gelatin hardener.

The second object of the present invention is to provide a gelatin hardening agent which has a fast hardening effect on gelatin and a small amount of post-hardening. A third object of the present invention is to provide a hardener useful as a gelatin hardener having improved properties of the photographic light-sensitive material.

[0008]

As a result of intensive studies, the present inventors have found that the above object can be achieved by using a compound represented by the following general formula (I) as a hardening agent for gelatin.

General formula (I)

[0010]

[Chemical 2]

In the formula, A represents an oxygen atom or a sulfur atom.
R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Those groups may be substituted. Also R ¹ and R
² is a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom, -C
(= O) -, - SO 2 -, - C (= S) - it may form a ring via a. When it contains a nitrogen atom, -CH ₂
The SO ₂ CH═CH ₂ group may be substituted.

More specifically, R ¹ and R ² are hydrogen atoms or preferably have ¹ or less carbon atoms which may be linear or branched.
-10 alkyl group (eg, methyl group, ethyl group, isopropyl group, butyl group, 2-ethylhexyl group), aryl group having 6 to 20 carbon atoms (eg phenyl group, naphthyl group), aralkyl having 7 to 20 carbon atoms The groups (for example, benzyl group and phenethyl group) may be the same or different. Particularly preferably, R ¹ and R ² are a hydrogen atom and an alkyl group having 1 to 3 carbon atoms.

R ¹ and R ² may be substituted,
As the substituent, a halogen atom (eg, chlorine atom), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group), an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy group)
Is preferred. Further, it is also preferable that R ¹ and R ² are combined to form a ring. A particularly preferred example is the case of forming a 5- or 6-membered ring.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

Next, synthetic examples of these compounds of the present invention will be shown. Synthesis Example 1 [Synthesis of Compound H-1] (Synthesis of N, N'-bis (2-chloroethylsulfonylmethyl) urea) Sodium sulfite (14 g) and sodium hydrogen carbonate (1
3.8g) dissolved in water (90ml) under ice cooling to 2
-Chloroethanesulfonyl chloride (18g) was slowly added dropwise. After dropping, the mixture was stirred for 50 minutes as it was, and then 49% H ₂ SO ₄ (10 g) was slowly added dropwise under ice cooling. After stirring for 50 minutes as it is, N,
N'-Dimethylol urea (4.8 g) was added and left overnight. The precipitated crystals were collected by filtration and dried to obtain the desired product. (Yield 9 g) (Synthesis of Compound H-1) N, N′-bis (2-chloroethylsulfonylmethyl)
Triethylamine (11.3 g) was slowly added dropwise to a solution of urea (19 g) in dimethylformamide (50 ml) under ice cooling. After dropping, the mixture was reacted at room temperature and then water (5
(0 ml) was added and the mixture was ice-cooled, and the precipitated crystals were collected by filtration and dried to obtain the desired product. (Yield 9g) Chemical structure is NM
It was confirmed by R spectrum, IR spectrum and elemental analysis.

Synthesis Example 2 [Synthesis of Compound H-4] (Synthesis of N, N'-bis (2-chloroethylsulfonylmethyl) ethyleneurea) Sodium sulfite (28 g) and sodium hydrogencarbonate (2
2-Chloroethanesulfonyl chloride (36 g) was slowly added dropwise to a liquid prepared by dissolving 7.6 g) in water (90 ml) under ice cooling. After the dropwise addition, the mixture was stirred for 50 minutes as it was, then ethylene urea (4.7 g) and 37% formaldehyde (17.8 g) were added, the pH was adjusted to 2.5 to 3.0 with formic acid, and the mixture was left at room temperature overnight. The precipitated crystals were collected by filtration and dried to obtain the desired product. (Yield 19 g) (Synthesis of compound H-4) N, N'-bis (2-chloroethylsulfonylmethyl)
Acetonitrile (60m) of ethylene urea (7.3g)
1) Triethylamine (4 g) was slowly added dropwise to the solution under water cooling. After dropping, the mixture was reacted at room temperature for 2 hours, water (30 ml) was added, and the precipitated crystals were collected by filtration and dried to obtain the desired product. (Yield 3.2g) Chemical structure is NM
It was confirmed by R spectrum, IR spectrum and elemental analysis.

Compounds other than the above-mentioned synthetic examples can also be synthesized by these methods or their similar methods. When these compounds are applied to gelatin-containing photographic layers as hardeners, deterioration of photographic properties such as deterioration of adhesiveness and reduction of photosensitivity is hardly observed.

[0020]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example-1 A compound of the present invention and a comparative compound were added to a 7% aqueous gelatin solution at the ratios shown in Table 1, and uniformly coated on a cellulose triacetate support so that the dry film thickness was about 8μ, It was further dried to prepare gelatin films (A) to (G). A gelatin film (H) containing no such hardener was also prepared as a control. These samples are placed in an environment of 25 ° C and 50% humidity, and after a lapse of 2 hours, 1 day, 3 days, and 7 days after application, a part of each sample is taken out and the following method is used. Number of crosslinks (crossli
The number of crosslinking units δ (number of crosslinking units per weight average molecular weight of gelatin before crosslinking) was determined. (How to obtain cross-linking number δ) Each gelatin film was separated from the support, and its weight and M ₁ were measured. The sol content was extracted from these gelatin films with warm water, and the gelatin amount, M _2, was determined by the microbiuret method. From these results, the sol fraction and S were calculated according to the following equation.

S = M ₂ / M _{1 From the} calculated value of S, A. "Atomic Radiation" by Charles By
and Polymers "(Atomic Ration and Polymers), Pergamon P
δ was calculated according to the following formula described on pages 134-158, published by Less (1960). δ = 2 / (S
+ S ^1/2 ) Table 1 shows δ of gelatin films (A) to (H) at each elapsed time.

The results are shown in Table 1.

[0023]

[Table 1]

As is clear from the results shown in Table 1, all gelatin films using the curing agent of the present invention have a fast curing action.
After applying and drying for 3 days or more, δ hardly changes. Further, in the gelatin films A and B using the comparative compound, the hardening action was slow, and δ increased after 3 days (post-hardening).
I understand.

From the above results, the compound H-
It is clear that all of 1, H-4, H-6, and H-10 are curing agents having a fast curing action. Example-2 The undercoat first layer of the following formulation- (1) and the second undercoat layer of the following formulation- (2) were sequentially coated on both surfaces of a biaxially stretched polyethylene terephthalate support having a thickness of 100 µm. Prescription- (1) Undercoat 1st layer Vinylidene chloride latex 15 parts by weight (core shell type latex water dispersion core part 90% by weight, shell part 10% by weight) Core part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile : Acrylic acid (93: 3: 3: 0.9: 0.1) shell part vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (90: 3: 3: 2: 2) 2,4-dichloro- 6-Hydroxy-S-triazine 0.25 parts by weight Polystyrene fine particles (average particle size 3 μ) 0.05 〃 Distilled water is added 100 〃 Further, 10 wt% KOH is added, pH = 6 ± 0.3
Adjusted to.

This coating solution was applied at a liquid temperature of 10 ° C. and a drying temperature of 180.
The coating was applied so that the dry film thickness was 1 μm at 2 ° C. for 2 minutes. Formulation- (2) Undercoat second layer Gelatin 1 part by weight Methylcellulose 0.05 〃 Compound-1 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound-2 3.5 × 10 ^-3 〃 acetic acid 0.2 〃 water was added 100 〃 This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness would be 0.1 µm.

On one side of the thus obtained support, two layers of a conductive layer and a back layer having the following formulations-(3) and-(4) were simultaneously coated in multiple layers. Formulation- (3) Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 300 mg / m ² Gelatin 170 〃 Compound-2 7 〃 Dodecylbenzenesulfonic acid sodium salt 10 〃 Dihexyl-α-sulfo Succinate sodium salt 40〃 Polystyrene sulfonic acid sodium salt 9〃

Formulation- (4) Back layer Gelatin 2.9 g / m ² compound-3 300 mg / m ² compound-4 50〃 compound-5 50〃 compound-2 10〃 dodecylbenzenesulfonic acid sodium salt 70〃 dibenzyl-α -Sulfosuccinate sodium salt 15 〃 Hardener shown in Table 2.

Ethyl acrylate latex (average particle size 0.05 μ) 500 〃 Perfluorooctane sulfonic acid lithium salt 10 〃 Silicon dioxide fine powder particles 35 〃 (Average particle size 4 μ, pore diameter 170 Å, surface area 300 m ² / g) Furthermore, the following prescription- (5), (6),
Silver halide emulsion layers-1 and -2 and protective layers-2 and -3 of (7) and (8) were sequentially coated. Formulation- (5) Silver halide emulsion layer-1 liquid I; water 300 ml, gelatin 9 g liquid II; AgNO ₃ 100 g, water 400 ml III liquid; NaCl 37 g, (NH ₄ ) ₃ RhCl ₆
1.1 ml and 400 ml of water Solution II and solution III were simultaneously added to solution I kept at 45 ° C. at a constant rate. After removing soluble salts from this emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. This emulsion was a monodisperse emulsion with an average grain size of 0.20 μ, and the emulsion yield was 1 kg.
The amount of gelatin contained per hit was 60 g.

The following compounds were added to the emulsion thus obtained. Compound -6 6 × 10 ^-3 mol / Ag1 mole compound -7 60 mg / m ² Compound -8 9 mg / m ² Compound -2 10 mg / m ² Sodium polystyrene sulfonate 40 mg / m ² N-oleoyl -N- Methyl taurine sodium salt 50 mg / m ² 1-Phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.05 μ) 0.46 g / m ² The coating solution thus obtained is coated silver Amount 1.3g / m ²
Was applied so that Formulation - (6) The silver halide emulsion layer -2 I solution; water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400 ml III _{solution; NaCl 37g, (NH 4)} 3 RhCl 6
2.2 mg, water 400 ml Formulation II and III in the same manner as in the emulsion of (5).
The liquid was added simultaneously to prepare an emulsion. This emulsion was a monodisperse emulsion having an average grain size of 0.20μ.

The following compounds were added to the emulsion thus obtained. Emulsified Dispersion of Hydrazine Derivative Compound-6 as 5 × 10 ⁻³ mol / Ag 1 mol Compound-7 60 mg / m ² Compound-8 9 mg / m ² Compound-2 10 mg / m ² Polystyrenesulfonic acid sodium salt 50 mg / m ² N-oleoyl-N-methyltaurine sodium salt 40 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.40 g / m ² thus obtained The applied coating liquid was coated with an amount of silver of 1.3 g / m ²
Was applied so that Formulation - (7) protective layer-2 Gelatin 1.0 g / m ² lipoic acid 5 mg / m ² sodium dodecylbenzenesulfonate 5 mg / m ² Compound -9 20 mg / m ² of polystyrene sulphonic acid sodium salt 10 mg / m ² compound-10 20 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 200 mg / m ² formulation- (8) protective layer-3 gelatin 1.0 g / m ² fine particles of silicon dioxide (average particle size) 2.0 μ) 50 mg / m ² dodecylbenzenesulfonic acid sodium salt 20 mg / m ² perfluorooctanesulfonic acid potassium salt 10 mg / m ² N-perfluorooctanesulfonyl-N-propyl glycine potassium salt 3 mg / m ² Curing agent As shown in Table 2.

Polystyrene sulfonic acid sodium salt 2 mg / m ² poly (degree of polymerization 5) oxyethylene nonyl phenyl ether sulfate ester sodium salt 20 mg / m ² <Method for preparing emulsified dispersion of hydrazine derivative> Liquid I: Compound-6 3 0.0g Compound-11 1.5g Poly (N-tert-butylacrylamide) 6.0g Ethyl acetate 30ml Sodium dodecylbenzenesulfonate 0.12g (72% methanol solution) Water 0.12ml It was made to melt and it was set as the liquid I.

Solution II: Gelatin 12 g, Compound-2 0.02 g, Water 108 ml, heated to 65 ° C. and uniformly dissolved to obtain Solution II.

Liquids I and II were mixed and stirred at high speed with a homogenizer (manufactured by Nippon Seiki Seisakusho) to obtain a fine particle emulsion dispersion. This emulsion was heated under reduced pressure to remove ethyl acetate, and then water was added to 250 g. The residual ethyl acetate was 0.2%.

The chemical structural formulas of compounds-1 to 11 used in the present invention are shown below.

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

After coating and drying, the product was allowed to stand in an atmosphere of 25 ° C. and 40% RH (absolute humidity 0.79%) for 2 hours and then hermetically sealed. Inventive product 8 disclosed in Example-1 of JP-A-61-189936 was used as the moisture-proof bag.

After leaving the sample sealed in a moisture-proof bag in an atmosphere of 25 ° C., the following methods were used for 7 weeks (1) wet film strength, (2) dryness by automatic processor treatment, (3) adhesion resistance. The sex was evaluated. Wet film strength evaluation method (1) Wet film strength After immersing the sample in distilled water at 25 ° C for 5 minutes, it was pressure-bonded to the sample film surface with a needle equipped with a steel ball having a radius of 0.4 mm at the tip, and 10 mm / sec. The load of the needle was continuously changed while moving at a speed, and the load (g) when the film was broken (that is, scratches were generated on the sample film surface) was measured. (2) Evaluation method of dryness by automatic development processing A film of size 50.8 × 61 cm ² was heated at 30 ° C. 80%
It was judged from which sheet the sheet became undried when 10 sheets were continuously processed under the RH environment.

To determine the dry state, the film surface was touched by hand to determine the dampness. (3) Adhesion resistance test Each sample was cut into 3.5 cm × 3.5 cm, two sets were made into one set, and the humidity was adjusted at 25 ° C. 80% RH (relative humidity) for 2 hours, and then the back layer of the same set of samples was used. The protective layer was brought into contact, a load of 1 kg was applied, and the mixture was left at 35 ° C. and 75% RH for 24 hours. Next, the load was removed, and the area of the part that was peeled off and bonded between the back layer and the protective layer (in the protective layer, the part colored with the dye transferred from the back layer) was calculated.

The adhesion resistance was evaluated according to the following criteria. Rank A The area ratio of the bonded portion is 0 to 25%, Rank B is 〃 26 to 50%, Rank C is 〃 51 to 75%, Rank D is 〃 76% or more, or the adhesive force cannot be peeled off strongly.

The results are shown in Table 2.

[0045]

[Table 2]

As is clear from Table 2, the use of the curing agent of the present invention improves the adhesion resistance without deteriorating the wet film strength and the drying property.

[0047]

According to the gelatin hardening method of the present invention, it is possible to carry out hardening of gelatin which has a fast hardening action and completes the hardening reaction early.

The method for hardening gelatin of the present invention is used in a method for hardening a photosensitive layer of a photographic light-sensitive material, which has a high hardening speed, little post-hardening and does not adversely affect the properties of the photographic material.
Hardening of a suitable photosensitive layer can be performed.

Claims (1)

[Claims] 1. A method for hardening gelatin, which comprises using at least one compound represented by the following general formula (I). General formula (I): In the formula, A represents an oxygen atom or a sulfur atom. R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Those groups may be substituted. R ¹ and R ² are carbon atoms,
Nitrogen atom, sulfur atom, oxygen atom, -C (= O)-, -S
_{O 2 -, - C (=} S) - it may form a ring via a. When containing the nitrogen atom, -CH ₂ SO ₂ CH = CH
_Two groups may be substituted.