JPS601615B2 - How to harden gelatin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gelatin curing method using a novel hardening agent, and particularly to a gelatin curing method suitable for curing gelatin films of photographic light-sensitive materials.

Generally, photographic materials include, for example, a silver halide emulsion layer,
It consists of various layers such as a filter layer, intermediate layer, protective layer, subbing layer, backing layer, ultraviolet absorbing layer, and antihalation layer on a suitable support such as glass, paper, or synthetic resin film. Moreover, these various constituent layers are composed of a so-called gelatin film mainly composed of gelatin.

Therefore, the physical properties of the constituent layer mainly consisting of gelatin film are as follows.
It mainly depends on the physical properties of gelatin.

By the way, the properties of gelatin itself, such as a low melting point, excessive water swelling, and weak mechanical strength, are fatal drawbacks in terms of the physical properties of the constituent layers of photographic light-sensitive materials. For this reason, the physical properties of gelatin have been improved by applying various stiffening agents to gelatin to cause a crosslinking reaction with functional groups such as amino groups, carboxyl groups, and amide groups in gelatin molecules. There is.

A number of compounds are known to be effective for hardening gelatin and increasing the water resistance, heat resistance and scratch resistance of the gelatin layer. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Pat.
74723 "Reactive halogen-containing compounds described in 1167207, etc., ketone compounds such as diacetyl and cyclobentanedione, pis(2-chloroethylurea), 2-hydroxy-4,6-dichloro-1・3,5 triazine, sivinyl sulfone, 5-acetyl-1,3-diacryloyl, hexahydro-1・
3,5-triazine, U.S. Pat. No. 3,635,718, 3
232763, compounds with reactive olefins described in British Patent No. 994809, N-hydroxymethylphthalimide, and other US Patent No. 27323
16, N-methylol compounds described in U.S. Patent No. 2586168, etc., isocyanates described in U.S. Patent No. 3103437, etc., U.S. Patent No. 3017280
, aziridine compounds described in U.S. Pat. No. 2983611, etc., acid derivatives described in U.S. Pat. No. 2,725,294, U.S. Pat.
4 etc., epoxy compounds described in U.S. Patent No. 3091537 etc., isoxazole compounds described in U.S. Patent No. 332131 and 3543292 etc., mucochloric acid etc. halogen carboxaldehydes, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate, and chromium trichloride.

However, when these known hardening agents are used in photographic light-sensitive materials, they do not have a sufficient hardening effect, or the hardening effect occurs over a long period of time due to the so-called "posterior hardening", which occurs due to a slow hardening reaction to gelatin. Changes, adverse effects on the properties of photographic materials (especially increased fog, decreased sensitivity, etc.)
(softening of tone, reduction of maximum density, etc.), or the coexistence of other photographic additives that may cause a loss of hardening action or the effectiveness of other photographic additives (e.g., couplers in internal color emulsions). those that reduce or pollute;
All of them have some drawbacks, such as the compounds used are difficult to synthesize and cannot be synthesized in large quantities, and the hardening agents themselves are unstable and have poor storage stability. In recent years, there has been a demand for rapid processing of photographic materials, and for this reason, progress has been made to improve the photographic materials themselves to meet the rapid processing requirements and to improve processing solutions suitable for such photographic materials.

For example, for the purpose of rapid penetration of processing liquids, the amount of gelatin in photographic light-sensitive materials has been reduced to make the layers thinner. However, this not only deteriorates the physical properties of the film but also increases fog. Therefore, as high-temperature, short-time processing using automatic processing machines and strong processing liquids becomes widespread, there is a demand for films with strong mechanical strength and physical properties that do not impair photographic properties. The object of the present invention is to provide a new hardening agent that does not cause the various disadvantages mentioned above, and a method for curing gelatin, particularly suitable for hardening gelatin films of photographic light-sensitive materials, using this hardening agent. is to provide.

Other objects and features will be apparent from the description below. The above object is achieved by using a compound represented by the following general formula as a hardening agent for gelatin.

General formula [wherein, X represents a halogen atom, Y represents an oxygen atom, a sulfur atom or a methylene group, and R represents a methylene group represented by or a phenylene group represented by .

Here n' is 2, 3 or 4, and R. is a hydrogen atom,
Halogen atom or alkyl group (preferably 1 to 5 carbon atoms)
alkyl group).

R2 is a hydrogen atom, an alkyl group (preferably a carbon number of 1 to
5 alkyl group), alkoxy group (preferably 1 carbon number)
-5 alkoxy group), carboxyl group or sulfo group. Next, examples of compounds represented by the above general formula are shown,
The compounds of the present invention are not limited to these.

H-1 H-2 H-3 H-4 H-5 H-6 day 7 H-8 H-9 H-10 Examples of synthesis of compounds used in the present invention are shown below.

Synthesis Example 1 (Illustrated Compound H-3) After dissolving 8.7 parts of 2-oxolidone in 50 parts of acetonitrile, 10.4 parts of phosphorus pentachloride was added, and the mixture was heated at room temperature for 6 hours.

Thereafter, the mixture was heated under reflux for 1 hour, and after cooling, 2 parts of water were added and the mixture was stirred for a while, and then the solvent was distilled off under reduced pressure. 30 parts of dioxane was added to the residue for crystallization, followed by washing with cyclohexane and drying.

Yield: 7.51 ta Melting point: 196-196.5 o 0 Elemental analysis calculation value C: 28.31 grand H: 3.17* N:
11.00*Measurement value C: 28.26% H: 3.08
Multi-N: 10.87% The gelatin curing method of the present invention includes all forms in which the compound according to the present invention and gelatin are contacted and reacted, and particularly in a layered gelatin film that is a component of a photographic light-sensitive material. Forms in which the compound and gelatin are allowed to interact include a method in which the compound is added to a coating solution, coated, and dried, and a compound that has been preliminarily reacted with gelatin is added to a coating solution, and then coated and dried. Method,
A method in which a coating solution containing the compound is applied to a layer that has already been applied to form a layer and then dried, a method in which the component is applied and then immersed in a solution in which the compound is dissolved, and a development process. A method such as immersion in a solution containing this compound before or during the process can be used.

When the hardener according to the present invention is added to a coating solution for forming a gelatin film, the amount added will vary depending on the type, physical properties, photographic properties, etc. of the intended gelatin film, but in general, it will be added to the coating solution. of gelatin, from 0.01 to 100% by weight of the dry state amount of gelatin, preferably from 0.1 to 1% by weight.

The addition time may be at any stage of preparing the coating solution for forming the gelatin film, but for example, when adding it to a silver halide emulsion, it is generally added after the second ripening of the silver halide emulsion. It is better to do so. More preferably, it is added immediately before coating. When the hardener according to the present invention is applied to the gelatin film of a silver halide photographic light-sensitive material, it exhibits effective hardening properties without impairing photographic properties such as fog or sensitivity of the photographic emulsion, and Because there is extremely little post-during film, it is possible to obtain photographic materials of stable quality, and even when the photographic materials are stored for long periods of time, it does not adversely affect the photographic emulsion, providing more effective stability. Provides excellent hardness that can withstand high-temperature rapid processing and automatic processing.

The hardening agent according to the present invention may be used alone, but if necessary, two or more types can be used in combination, and furthermore, they can be used in combination with the above-mentioned known hardening agents.

The silver halide photographic material to which the present invention can be applied may be, for example, any type of black and white photographic material, color photographic material, or false color photographic material;
In addition to photographic materials used for various purposes such as printing, X-rays, and radiation, mechanically all kinds of photographic materials such as negative type, positive type, and diffusion transfer type can be mentioned.

The gelatin to which the hardening agent of the present invention is applied may be partially composed of colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, and sugar derivatives such as starch derivatives. Synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof, partial hydrolysates, etc. can be substituted, as well as so-called gelatin derivatives, i.e., those contained in the molecule. amino groups, imino groups, hydroxyl groups, and carpoxyl groups as functional groups treated and modified with a reagent that has one group that can react with them, or bonded with molecular chains of other polymeric substances. It may be replaced with a graft polymer.Silver halide photographic light-sensitive materials can be exposed to all types of silver halides such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. It can also be used as a component, and can also be used for sensitization with salts of noble metals such as ruthenium, palladium, rhodium, platinum, and gold, sulfur sensitization with sulfur compounds, selenium sensitization with selenium compounds, reduction with stannous salts, polyamines, etc. Various chemical sensitizations such as sensitization or further sensitization with polyalkylene oxide compounds can be carried out.Furthermore, optical sensitization can be carried out with cyanine dyes, merocyanine dyes, etc. compounds, stabilizers such as azaindene compounds and benzothiazoyl compounds, wetting agents such as dihydroxyalkanes, antistatic agents, ultraviolet absorbers, water-dispersible fine particulate polymeric substances obtained by emulsion polymerization, saponins, Polyethylene glycol lauryl ether, sodium dodecylbenzenesulfonate, Japanese Patent Publication No. 48-431, published in 1984-930.
Coating aids such as fluorosurfactants such as No. 30 and various other known photographic additives may be added. Supports for photographic materials to which the curing method of the present invention is applied include, for example, paper, laminated paper, glass, cellulose acetate, cellulose night, polyester, polyamide,
Films, sheets, etc. of polystyrene etc. may be used.

The present invention will be explained below by giving examples.

Example 1 Silver bromide 65.5 mol% "Silver chloride 34.0%, Silver iodide 05
A silver iodochlorobromide gelatin emulsion having a mole % composition and an average grain size of 0.45 French was prepared by a neutral single jet method.

After physical ripening, desalt by washing with water, add gelatin,
Next, sodium thiosulfate was added to perform chemical sensitization, and then a stabilizer and a surfactant were added to finish the emulsion. The resulting gelatin-silver halide emulsion was divided into 7 parts. 1
~4 parts of each of the above-mentioned exemplified compounds was added to 1 part of gelatin to 0.0 parts.
2 mmol was added, and the remaining 3 parts were used for comparison.Formaldehyde (comparison A) was added to one part, and 0.2 mmol of the compound represented by the formula (comparison B) was added to the other part, per gelatin. , no hardener was added to the remaining part (comparison C)
).

The seven types of emulsions obtained were coated on a photographic paper base coated with polyethylene layers on both sides as silver nitrate at a rate of 3.0 mm and gelatin at a rate of 5.0 mm. 40 pieces of the obtained sample
00 for 5 days. After exposing a portion of each sample to light through a step light sliding door, 1
It was developed between two inkstone sands, stopped, fixed, washed with water, and dried to determine photographic properties.

Developer water 750 Metol 1.02 Hydroquinone
4.0 ta sodium sulfite
15.0 Sodium carbonate (monohydrate) 26.7 Potassium bromide
Add 0.7 liters of water to make 1,000 ml of water. Next, another part of each sample was washed with the above developer for 200 ml of water without exposing it to light.
The film was developed for 10 minutes and checked for fog.

The results obtained are shown in Table 1.

As is clear from these results, the compound of the present invention shows extremely little decrease in maximum density, softening of tone (decreasing in gamma value), and little fog, and there is no adverse effect on photographic properties. I understand.

Example 2 A portion of the seven types of samples obtained in Example 1 was immersed in the developer, heated, and the temperature at which the emulsion film melted was measured to determine the melting point as a measure of hardness. Ta.

Furthermore, after immersing the remaining sample pieces in the developer solution at 20°C for 120 seconds, a pole point needle with a diameter of 0.5 was set perpendicular to the sample film surface, and a load was applied to the sample surface by 1 skin/skin. sec
Mechanical strength was determined by determining the load that caused damage to the surface of the sample film when it was moved in parallel at a speed of .

The results are shown in the table below.

U As is clear from Table 0, the compounds of the present invention exhibit extremely excellent hardening action.

Claims (1)

[Scope of Claims] 1. A method for curing gelatin, which comprises reacting a compound represented by the following general formula with gelatin. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a halogen atom, Y represents an oxygen atom, sulfur atom, or methylene group, and R is represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a methylene group represented by ▲Numerical formula, chemical formula, table, etc.▼ where n is 2.3 or 4, R_1 is a hydrogen atom,
It represents a halogen atom or an alkyl group, and R_2 represents a hydrogen atom, an alkyl group, an alkoxy group, a carboxyl group, or a sulfo group. ).