JPS6328295B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a gelatin curing method using a novel curing agent, and particularly to a gelatin curing method suitable for curing a gelatin film of a silver halide photographic light-sensitive material. Generally, photographic materials have various layers such as a silver halide emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer.
It is formed by layering on a suitable support such as glass, paper, or synthetic resin film, and these various constituent layers are composed of so-called gelatin membranes mainly composed of gelatin. Therefore, the physical properties of the constituent layer made of gelatin film mainly depend on the physical properties of gelatin.
By the way, the properties of gelatin itself, such as a low melting point, water swelling property, and weak mechanical strength, are
This is a fatal defect in terms of the physical properties of the constituent layers of photographic materials. For this reason, various hardening agents have traditionally been applied to gelatin to harden the amino groups in gelatin molecules.
The physical properties of gelatin have been improved by crosslinking it with functional groups such as carboxyl groups and amide groups. Examples of such hardeners include inorganic hardeners made of polyvalent metal salts such as chromium alum, chromium trichloride, aluminum sulfate, and zirconium sulfate; aldehyde compounds such as formalin and glyoxal; and US Pat. No. 3,288,775. ,
British Patent No. 2732303, British Patent No. 974723, British Patent No. 1167207
No., French Patent No. 2001599, Tokukosho
No. 47-6151, Special Publication No. 13709 (1973), Special Publication No. 13709 (1973)
Reactive halogen-containing compounds described in Publication No. 139689, etc., U.S. Patent No. 3635718,
Compounds with reactive olefins described in U.S. Patent No. 3232763 and British Patent No. 994809, N-methylol compounds described in U.S. Patent No. 2732316 and U.S. Patent No. 2586168, etc.
Aziridine compounds described in U.S. Patent No. 3017280 and U.S. Patent No. 2983611, etc.,
-22089, Japanese Patent Publication No. 53-118486, Japanese Patent Publication No. 54-7320, etc., carbodiimide compounds described in U.S. Patent No. 3100704 and others, U.S. Patent No.
Epoxy compounds described in specification No. 3091537 and elsewhere, U.S. Patent Nos. 3321313 and 3543292
isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane,
Dioxanes such as dichlorodioxane are known. However, when these known hardening agents are used in photographic light-sensitive materials, some of them do not have sufficient hardening effect, and some have a long-term change in hardening effect called "postdural" which occurs due to the slow hardening reaction to gelatin. Some substances have an adverse effect on the properties of photographic light-sensitive materials (in particular, increase in fog, decrease in photosensitivity, change in gradation, etc.), or coexist with other photographic additives (for example, couplers in internal color emulsions) The curing effect is too rapid and makes it difficult to produce photographic materials. The compounds used are difficult to synthesize and cannot be synthesized in large quantities. The curing agent itself is unstable and has poor storage stability. All of them have some drawbacks, such as those that do not have sufficient solubility in water and cause non-uniformity in photographic materials when used. In recent years, there has been a demand for rapid processing of photographic materials, and for this reason, progress has been made in improving the photographic materials themselves so that they can be rapidly processed and in processing solutions suitable for such photographic materials. For example, for the purpose of rapid penetration of a processing solution, the amount of silver halide in a photographic light-sensitive material is increased and the amount of gelatin is decreased to make the layer thinner.
However, this is accompanied by an increase in fog, and moreover, the physical properties of the film tend to deteriorate. This also goes against the demand for coatings with high mechanical strength that can withstand severe mechanical abrasion as automatic processing machines become more widespread. Moreover, as high-temperature, rapid processing using strong processing liquids has become widespread, strong film properties that do not impair photographic properties are required. In particular, in the processing of color films, color development itself takes more time than black and white development and usually requires bleaching, and in reversal color processing, a first development is also required, so a strong hardening film is required. For this reason, many of the curing agents conventionally known as excellent curing agents have various drawbacks as the rapid processing of photographic materials progresses.
For example, simply increasing the amount of gelatin added in order to obtain stronger film properties not only causes desensitization and increased fog, but also reduces the covering power or increases the hardness of the film. However, the film tends to be brittle, making it difficult to use in automatic processing machines, and other various drawbacks. Incidentally, cyanuric chloride has been proposed as a hardening agent for gelatin. However, this compound is highly reactive and has the undesirable property that when added to an aqueous gelatin solution, it not only immediately causes an undesirable increase in viscosity, but also causes irreversible coagulation. French patent no.
Dichloro-s-triazine derivatives are proposed in the specification of No. 2001599, but since these curing agents have low water solubility when used, it is necessary to dissolve them in various organic solvents and then add them to photographic components. It cannot be used unless you do so. Particularly when large amounts of organic solvents are present in photographic components, they often cause gelatin to coagulate and precipitate or cause coating failures, and in multilayer films such as color photographic emulsions, interlayer mass transfer is inhibited. This will cause the color to become cloudy. In addition, when a high boiling point solvent is used for dissolution, the drying time of the film is delayed and the solvent remains in the film even after drying, resulting in a decrease in film surface strength, deterioration of photographic properties during storage, and It is easy to cause adhesion among comrades. Furthermore, the use of organic solvents poses major safety and environmental problems in the manufacturing process. Subsequently, as a cyanuric chloride curing agent with excellent water solubility, 2,4-dichloro-6-sulfoanilino-s-triazine, as described in Japanese Patent Publication No. 39-16928, was published in Japanese Patent Publication No. 47-6151. 2,4-dichloro-6- as described
Water-soluble salt of hydroxy-s-triazine, JP-A-Sho
2,4 as described in Publication No. 53-139689
An aqueous solution of a partial hydrolyzate of -dichloro-6-alkoxy-s-triazine has been proposed.
These hardeners have considerably improved the drawbacks of the cyanuric chloride hardeners mentioned above, and the reaction to harden gelatin is completed more quickly than other types of hardeners for gelatin. It takes several days for the gelatin to completely harden. Therefore, when these hardening agents are used in layers constituting photographic light-sensitive materials, a post-hardening phenomenon occurs.
In addition, the physical properties of the film cannot be said to be satisfactory for high-temperature rapid processing and automatic processing using strong processing liquids, which have become popular in recent years. One of the objects of the present invention is to provide new hardening agents for hardening gelatin. Furthermore, another object of the present invention is to provide a hardening agent which is improved in almost all the drawbacks of the conventional hardening agents as mentioned above, and to use this hardening agent to prepare gelatin, especially for photographic materials. An object of the present invention is to provide a gelatin curing method suitable for curing gelatin films. The object of the present invention is to provide at least one 4,6-dichloro-s-triazine bonded to the 2-position via a nitrogen atom in the molecular structure and a 4,6-dichloro-s-triazine bonded to the 2-position via an oxygen atom in the molecular structure. - achieved by using a partial hydrolyzate of a compound containing at least one triazine as a hardening agent for gelatin. At least one 4,6-dichloro-s-triazine bonded to the 2-position via a nitrogen atom and 4,6-dichloro-s-triazine bonded to the 2-position via an oxygen atom in the molecular structure of the raw material of the partial hydrolyzate of the present invention. 6-dichlor-
The compound having at least one s-triazine is preferably represented by the following general formula. In the formula, m and n are positive integers, X is a simple bond or an (m+n)-valent organic residue, and R is a hydrogen atom or an organic residue. Specifically, in the general formula, 5- or 6-membered heterocyclic residues containing a sulfur atom (e.g. pyrrole ring, pyrrolidine ring, pyridine ring, pyrimidine ring,
(furan ring, pyran ring, thiophene ring, etc.), a 5- or 6-membered aliphatic residue, or a group in which these groups are connected. Each of these groups may be linked via a heteroatom, such as a nitrogen atom, an oxygen atom and/or a sulfur atom, or a carbonyl group. Furthermore, each of these groups has a substituent group, such as a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyloxy group, a heterocyclic group, an acyl group, an acylamino group, and a carbamoyl group. , an ester group, a sulfonamide group, a sulfamoyl group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a sulfo group, etc., and the substituent is further substituted with the above-mentioned substituent. Good too. The organic residue represented by R is an aliphatic residue (for example, alkyl (methyl, ethyl, propyl, butyl, etc.), alkenyl (allyl, butenyl, etc.), etc.), aromatic residue (for example, benzene ring, naphthalene ring, etc.), It represents a 5- or 6-membered alicyclic residue or an acyl group (eg, acetyl, benzoyl, naphthoyl, methanesulfonyl, p-tosyl, etc.). Each of these groups may be a substituent, e.g.

[Formula] (R' is the same as R),

[Formula] Halogen atom, alkyl group, alkenyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, acyloxy group, heterocyclic group, acyl group, acylamino group, carbamoyl group, ester group, sulfonamide group , sulfamoyl group, nitro group,
hydroxyl group, cyano group, carboxyl group, amino group,
It may have a sulfo group or the like, and the substituent may be further substituted with the above-mentioned substituent. Further, a 5- or 6-membered heterocycle in which a part or all of R and , thiamorpholine ring, etc.). Here, using the gelatin as a hardening agent means to cause the hardening agent to react with the gelatin to be hardened. Methods of reaction include a method in which a hardening agent is added to the coating solution and the coating is dried, a method in which a hardening agent is preliminarily reacted with gelatin and then added to the coating solution and then coated and dried, and a method in which the hardening agent is preliminarily reacted with gelatin is added to the coating solution and then coated and dried. A method in which a coating solution containing a hardening agent is applied onto a gelatin layer that does not contain a hardening agent to form a layer, and then the hardening agent is diffused into the gelatin layer that does not contain a hardening agent and then dried. Various known methods can be used, such as immersion in a solution containing a curing agent, or immersion in a solution containing this curing agent before or during development. The dichloro-s-triazine derivative represented by the above general formula, which is a raw material for the curing agent of the present invention, is described in Journal of Heterocyclic Chemistry, No. 7.
vol., pp. 975-979 (1970) using an inorganic alkali such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. with cyanuric chloride. It can be synthesized from a compound having an amino group and a hydroxyl group. Also, Helvetica
Helvetica Chimica Acta No.
44, pp. 299-309 (1961), a compound in which only the amino group moiety was reacted with cyanuric chloride and a corresponding compound having an amino group and a hydroxyl group was synthesized. Patent No.
The remaining hydroxyl group is synthesized by further reacting with cyanuric chloride using an organic base such as triethylamine, diisopropylethylamine, pyridine, or 2,4,6-collidine in the same manner as described in No. 3454551. You can also do that. Furthermore, it can also be directly synthesized from cyanuric chloride and a compound having a corresponding amino group and hydroxyl group using the above-mentioned organic base in a manner similar to that described in the above-mentioned US Pat. No. 3,454,551. Compounds having an amino group and a hydroxyl group, which are raw materials for the dichloro-s-triazine derivative represented by the above general formula, include hydroxylamine, ethanolamine, N-methylethanolamine, N-methylethanolamine, and N-methylethanolamine.
-Allylethanolamine, N-phenylethanolamine, diethanolamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylthio)ethanol, 2-(2-aminoethylsulfonyl)ethanol, γ-amino- β-hydroxybutyric acid, 2-(2-aminoethylamino)ethanol, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, 2-
Amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane,
2,2'-(ethylenediimino)diethanol, o
-aminophenol, m-aminophenol, p
-aminophenol, p-amino-m-cresol, p-β-aminoethylphenol, 2-aminophenol-4-sulfonic acid, 2-amino-4
-chlorphenol, 2,4-diaminophenol, 4-(2-aminoethyl)pyrocatechol,
6-amino-1-naphthol, 2-aminocyclohexanol, N-β-hydroxyethylpiperazine, 4-hydroxypiperidine, 2-hydroxymethylpiperazine, 1-aminoethanol, N
-ethylethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2
-Amino-2-methyl-1-propanol, 5-
amino-2,2-dimethyl-1-pentanol,
2-amino-2-methyl-1,3-propanediol, N-2'-aminoethyl-n-propanolamine, 2-(2-aminoethylamino)isopropanol, 2,2'-[iminobis(ethyleneimino) ] Diethanol, D-α-amino-β-hydroxypropionic acid, DL-α-amino-γ-
Hydroxybutyric acid, o-amino-p-cresol,
2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 4-amino-2-nitrophenol, o-aminobenzyl alcohol,
p-aminophenethyl alcohol, 4-amino-
N-(β-hydroxyethyl)-N-ethylaniline, 3-amino-4-hydroxybiphenyl, 5
-amino-1,3-dihydroxybenzene, 2,
2'-[(m-aminophenyl)imino]diethanol, 3-aminosalicylic acid, 5-aminosalicylic acid, 5-amino-1-naphthol, 5-amino-
2-naphthol, 8-amino-2-naphthol,
1-amino-2-naphthol-4-sulfonic acid,
1-amino-5-naphthol-7-sulfonic acid,
2-amino-8-naphthol-6-sulfonic acid,
2-aminocyclopentanol, 1-aminomethylcyclopentanol, α-(aminomethyl)cyclohexanemethanol, 3-hydroxypiperidine amino sugars such as glucosamine, galactosamine, etc. Synthetic polymers having amino groups and hydroxyl groups, such as copoly(vinyl alcohol-vinylamine), copoly(hydroxystyrene-allylamine), and the like. In the general formula, m and n are not particularly limited as long as they are positive integers, but from the viewpoint of synthesis (ease of obtaining raw materials, ease of purification of intermediates, ease of partial hydrolysis, etc.) , preferably X is a simple bond, an (m+n)-valent aliphatic group having 2 to 10 carbon atoms (the carbon chain may contain a nitrogen atom, an oxygen atom and/or a sulfur atom), or an aromatic It is a (m+n) valent group derived from a group group, especially a benzene ring or a naphthalene ring, and R is a hydrogen atom,

[Formula] (R″ represents a hydrogen atom or a lower alkyl group) or

One of the formulas is a lower alkyl group or a lower alkenyl group that may have
(m+n) is 2, 3 or 4. Next, a typical example of the dichloro-s-triazine derivative represented by the above general formula, which is a raw material for the curing agent used in the present invention, will be given, but the raw material for the curing agent used in the present invention is limited. It's not something you can do. The curing agent used in the present invention is the dichloro-
The s-triazine derivative is treated with an alkali, such as sodium bicarbonate, sodium carbonate, potassium carbonate,
Sodium acetate, sodium hydroxide, potassium hydroxide, trisodium phosphate, tripotassium phosphate,
It can be obtained by treatment (partial hydrolysis) with an aqueous solution of triammonium phosphate, sodium metaborate and/or potassium metaborate, preferably at room temperature to 50°C. In this case, the dichloro-s-triazine derivative may be directly added to the alkaline aqueous solution for treatment, or the dichloro-s-triazine derivative
The s-triazine derivative may be dissolved in an organic solvent such as acetone or dioxane, and the solution may be added to an alkaline aqueous solution for treatment. Also, dichlor-s-
The amount of alkali used per mole of triazine derivative is (m+n+m'+n') x 1 to 6 equivalents (m
and n are the same as m and n in the above general formula, and m' and n' are R in the above general formula as a substituent.

[expression] or

[Formula] is the respective number when it has. )In Although,
Considering the partial hydrolysis rate and the storage stability of the resulting partial hydrolyzate, the amount of alkali is (m
+n+m'+n')×2 to 4 equivalents is preferred. The obtained solution of the partial hydrolyzate may be used as it is or diluted with water to an appropriate concentration.
In the case of an aqueous solution containing an organic solvent, only the organic solvent may be distilled off and the solution may be used as it is or after being diluted with water to an appropriate concentration. In some cases, the solution may be dried and used as a powder. The curing agent used in the present invention is obtained by isolating the dichloro-s-triacycin derivative, which is a raw material, when it is synthesized from cyanuric chloride and a compound having an amino group and a hydroxyl group using an inorganic alkali as a dehydrochlorination agent. It can also be obtained by subsequent treatment (partial hydrolysis) with the aqueous alkaline solution described above. When the hardening agent according to the present invention is added to a coating solution for forming a gelatin film, the amount added varies depending on the type, physical properties, photographic properties, etc. of the intended gelatin film, but in general, it About 5×10 ^-7 to 1 g of dry weight of gelatin
2.5×10 ⁻³ mol, preferably 5×10 ⁻⁶ to 2.5×10 ⁻⁴
It is a mole. It may be added at any stage of preparing a coating solution for forming a gelatin film, but for example, when added to a silver halide emulsion, it is generally added after the second ripening of the silver halide emulsion. Good. 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 that can be used for a variety of purposes, such as mechanically negative type, positive type, and diffusion transfer type photosensitive materials, all kinds of photosensitive materials can be mentioned. The silver halide emulsions used in these silver halide photographic materials include all types of halogenated emulsions such as silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Silver can be used as a light-sensitive component and the emulsion contains salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, gold, such as ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadite, potassium Various chemicals such as noble metal sensitization using chloroaurate, sulfur sensitization using sulfur compounds, selenium sensitization using selenium compounds, reduction sensitization using stannous salts, polyamines, etc., and further sensitization using polyalkylene oxide compounds. Sensitization can be performed. This emulsion can also be optically sensitized with cyanine dyes, merocyanine dyes, etc., and stabilizers such as couplers, mercury compounds, triazole compounds, azaindene compounds, benzthiazolium compounds, and zinc compounds. , wetting agents such as dihydroxyalkanes,
Antistatic agents, film property improvers made of water-dispersible fine particulate polymeric substances obtained by emulsion polymerization, coating aids such as saponin and polyethylene glycol lauryl ether, and various other photographic additives may also be added. can. Supports for photographic materials to which the curing method of the present invention is applied include, for example, paper, laminated paper, glass,
Films, sheets, etc. of cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, etc. are used, and are selected depending on the intended use of the photographic material. Although the curing agent according to the present invention may be used alone,
If necessary, two or more types can be used in combination, and furthermore, they can be used in combination with the above-mentioned known curing agents. The curing method of the present invention exhibits its characteristics more effectively when particularly advanced technology is required, such as color photographic light-sensitive materials. As mentioned above, color development used in the processing of color photographic materials requires a longer time than black and white development, and since a bleaching process is usually performed, the total processing time is longer. In the processing of reversal color light-sensitive materials, a first development is required thereon, and in the processing of external reversal color light-sensitive materials, further color development is repeated several times. Therefore, color photographic materials suitable for high-temperature processing are required to have a strong hardening film. According to the curing method of the present invention, it is possible to produce a film that can sufficiently withstand the above-mentioned treatments. Furthermore, since there is virtually no change due to aging or heat treatment, color photographic materials with stable performance without defects due to excessive hardening can be produced. Another feature of color photographic materials is that they have a complex composition and use a wide variety of compounds. The curing method of the present invention utilizes couplers such as 5-
Applicable to color photographic materials using pyrazolone-based magenta couplers, naphthol-based or phenolic-based cyan couplers, open-chain ketomethylene-type yellow couplers, or these so-called 2-equivalent or 4-equivalent couplers, and so-called masking couplers having an arylazo group at the active site. However, there is no color development problem that is often seen with other hardeners. In addition, if necessary, a color containing an ultraviolet absorber, a fluorescent whitening agent, a mordant layer, a dye developer, and a development inhibitor-releasing compound as described in Japanese Patent Publication No. 51-16141, etc. It is also effective when applied to photographic materials. Next, typical production examples of the curing agents used in the present invention will be shown. Production example 1 Dissolve 37g of sodium hydrogen carbonate in 600ml of water,
While stirring at 40° C., a solution of 35.7 g of N,O-bis(4,6-dichloro-S-triazin-2-yl)-2-aminoethanol (triazine compound example 2) in 500 ml of acetone is added dropwise. After dropping, the mixture is stirred at the same temperature for 2 hours until the triazine compound is completely dissolved. Filter the solution and remove the acetone under reduced pressure.
Adjust the total volume to 1000ml with water. Production example 2 95g of trisodium phosphate (12 hydrate) and 700ml of water
N,O-bis(4,6-dichloro-S-triazin-2-yl) while stirring at 35°C.
A solution of 35.7 g of -2-aminoethanol (triazine compound example 2) in 500 ml of acetone is added dropwise. After dropping, the mixture is stirred at the same temperature for 8 hours until the triazine compound is completely dissolved. Filter the solution, remove the acetone under reduced pressure, and adjust the total volume to 1000 ml with water. Production example 3 55g of sodium metaborate (tetrahydrate) and 700ml of water
N,O-bis(4,6-dichloro-S-triazin-2-yl) while stirring at 40°C.
A solution of 35.7 g of -2-aminoethanol (triazine compound example 2) in 500 ml of acetone is added dropwise. After dropping, stir at the same temperature for 10 hours until the triazine compound is completely dissolved. Filter the solution, remove the acetone under reduced pressure, and adjust the total volume to 1000 ml with water. Production example 4 Dissolve 37g of sodium hydrogen carbonate in 600ml of water,
While stirring at 40°C, add 40.5 g of N,O-bis(4,6-dichloro-S-triazin-2-yl)-3-aminophenol (triazine compound example 18.)
Add it little by little over a period of about 1 hour. Stir at the same temperature for 4 hours until the triazine compound is completely dissolved. Filter the solution and adjust the total volume to 1000ml with water. Production example 5 76g of trisodium phosphate (12 hydrate) and 550ml of water
N,O-bis(4,6-dichloro-S-triazin-2-yl) while stirring at 40°C.
-3-aminophenol (triazine compound example)
18) Drop a solution of 40.5g in 500ml of acetone. After dropping, stir at the same temperature for 12 hours until the triazine compound is completely dissolved. Filter the solution, remove the acetone under reduced pressure, and adjust the total volume to 1000 ml with water. Production example 6 85g of trisodium phosphate (12 hydrate) and 600ml of water
N, O, O′,
O″-tetrakis(4,6-dichloro-S-triazin-2-yl)-tris(hydroxymethyl)
A solution of 28.2 g of aminomethane (triazine compound example 15) in 400 ml of acetone is added dropwise. After dropping, stir at the same temperature for 10 hours until the triazine compound is completely dissolved. Filter the solution, remove the acetone under reduced pressure, and adjust the total volume to 500 ml with water. The curing agent used in the present invention has a favorable rate of curing reaction, so that it increases the viscosity of the gelatin solution until it is added to the gelatin solution and the solution is formed into a film. Never. Nevertheless, during drying after film formation, the curing reaction occurs very quickly, so that there is virtually no post-hardening phenomenon. Therefore, the gelatin film strength of photographic materials produced using this curing agent is constant immediately after production. Therefore, when comparing a photosensitive material immediately after production with a photosensitive material that has been aged, there is almost no difference in apparent sensitivity, change in color balance, etc. since there is no difference in the permeation rate of the developer during processing. In addition, the gelatin film strength of photographic materials produced using this hardening agent is much higher than when using the above-mentioned hardening agents, and is therefore sufficiently resistant to high-temperature rapid processing and automatic processing using strong processing liquids. It is possible to obtain the desired film physical properties. Further, the curing agent used in the present invention has extremely high solubility in water. This has a very important meaning. This is because the solubility in water is extremely low, so when producing photographic materials,
If organic solvents have to be used for the addition of hardeners, the various disadvantages mentioned above cannot be avoided. Furthermore, even if there is some solubility in water, the more water is required to add a hardening agent during the production of photographic light-sensitive materials, the greater the burden of drying that water becomes, resulting in energy consumption. Not only is this a loss, but more space and equipment are required for drying, which reduces productivity. Furthermore, in recent years, photographic light-sensitive materials have been manufactured at higher speeds, and for example, when using a slide coater and elastrusion coating, the gelatin or emulsion solution needs to have a certain high viscosity. However, adding a large amount of water to add a hardening agent naturally tends to lower the viscosity, which can even be fatal in some cases. Therefore, the high water solubility of the curing agent is a very important advantage for this industry, and moreover, this curing agent has a very strong curing effect per weight, so compared to other curing agents, it is Therefore, the amount of water added can be reduced even further. Furthermore, the curing agent used in the present invention does not interact with other photographic additives that coexist, such as color couplers for color sensitive materials, even during long-term storage of photographic light-sensitive materials. Does not reduce the effectiveness of additives or cause the curing agent to lose its curing ability. Moreover, it does not have an adverse effect on the properties of the photographic light-sensitive material (eg, increase in fog, decrease in photosensitivity, etc.). Note that the substances that can be hardened by the hardening agent of the present invention are not limited to gelatin, but include hydrophilic polymeric substances that have primary or secondary amino groups like gelatin, and gelatin and other hydrophilic substances. Mixtures with other polymeric substances can also be cured by the curing agents of the present invention. Next, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited to these examples, and various applications can be made. Example 1 Gold and sulfur sensitizers were added to a neutral process negative silver iodobromide emulsion containing 1.5 mol % of silver iodobromide, and a second ripening was carried out, and 4-hydroxy-6-methyl- was added as a stabilizer. After adding 1,3,3a,7-tetraazaindene, diethylene glycol as a wetting agent, and saponin as a coating aid, it was divided into 8 parts, one of which was applied to a polyester base and dried to serve as a control sample, and the remaining 7 Comparative curing agents (A) and (B) and curing agents of the present invention (1), (2), (3), (4), and (5) were added to the polyester base and dried. It was used as a sample. Comparative hardener (A) Mucochloric acid. Comparative curing agent (B) 2,4-dichloro-6-methoxy-S-triazine in an equimolar amount of trisodium phosphate (12 hydrate)
A curable solution partially hydrolyzed with an aqueous solution. (Curing solution described in JP-A-53-139689) Curing agent of the present invention (1) Aqueous solution of Production Example 1. Curing agent of the present invention (2) Aqueous solution of Production Example 2. Curing agent of the present invention (3) Aqueous solution of Production Example 3. Curing agent of the present invention (4) Aqueous solution of Production Example 4. Curing agent of the present invention (5) Aqueous solution of Production Example 6. The dura mater properties of these control samples and each sample were measured by the following method. That is,
After coating and drying each sample, temperature 25℃, relative humidity
Samples stored at 55% for 1, 3, 7, and 14 days, and heat treated at 50℃ and 80% relative humidity for 3 days, were immersed in a 1.5% sodium hydroxide solution kept at 50℃. The time required for the gelatin film to begin to dissolve was measured. In addition, a sample piece stored and heat-treated under the same conditions was immersed for 2 minutes in a 3% aqueous solution of sodium carbonate (monohydrate) at 25°C, and the surface of the gelatin film was immediately wiped off. The film was scratched with a saphire needle, and the load at the point when the film surface started to be scratched was measured and expressed as the film surface strength. Table 1 shows the results and the results of sensitometry and fog measurements performed on each sample, which was stored for one day at a temperature of 25°C and a relative humidity of 55% after coating and drying. Note that the sensitivity in the table is expressed as a relative value when the sensitivity of the control sample (sample No. 1) is set as 100.

【table】

[Table] As is clear from Table 1, the curing agent according to the present invention is superior to conventionally known comparative curing agents in both solubility resistance to alkaline liquid and film surface strength, and also has excellent photographic properties. It can be seen that it has an extremely excellent hardening effect with virtually no post-hardening caused by natural standing and heat treatment without any damage. Example 2 A multilayer film having the following layer structure was prepared on a cellulose acetate film base, and a control sample was prepared in which no curing agent was contained in any of the layers. 1st layer...halation prevention layer. Second layer: a red-sensitive silver halide gelatin emulsion layer containing a cyan coupler. 3rd layer...gelatin middle layer. 4th layer...magenta coupler and Tokko Sho 51-
A green-sensitive silver halide gelatin emulsion layer containing a development inhibitor-releasing compound described in Japanese Patent No. 16141. Fifth layer...filter layer containing yellow colloidal silver. 6th layer...A blue-sensitive silver halide gelatin emulsion layer containing a yellow coupler. 7th layer...gelatin protective layer. Separately comparative curing agents (A), (C) and curing agent of the present invention
Samples containing (2), (6), (7), and (8) were prepared. Comparative curing agent (C) (a) 2,2′-(ethylenedioxy)bis[4,6
-dichloro-S-triazine] in acetone solution. (b) An aqueous sodium bicarbonate solution in an equimolar amount to the triazine derivative in (a). After adding (a), add (b). (Curing method described in Japanese Patent Publication No. 48-13709) Curing agent of the present invention (6) Aqueous solution of Production Example 5. Curing agent of the present invention (7) N,O-bis(4,6-dichloro-S-triazin-2-yl)-2-(2-aminoethoxy)ethanol (triazine compound example 7) in the same manner as in production example 1. and partially hydrolyzed aqueous solution. Curing agent of the present invention (8) N,O,O'-tris(4,6-dichloro-S
An aqueous solution obtained by partially hydrolyzing -triazin-2-yl)-diethanolamine (triazine compound example 6) in the same manner as in production example 2. The hardness of each sample was measured in the same manner as in Example 1. Regarding photographic properties, 4-amino-3-methyl-
Color development was performed at 38 DEG C. for 3 minutes using a color developer containing N-ethyl-N-hydroxyethylaniline sulfate as the main ingredient, followed by bleaching, fixing, and washing in a conventional manner, followed by sensitometry. These results are shown in Table 2. Note that the sensitivities in the table are expressed as relative values when the sensitivity of the control sample (sample No. 9) is taken as 100 in sensitometry through each color filter. In addition, B in the table,
G and R indicate that sensitometry was performed by measuring color density through blue, green, and red filters, respectively.

【table】

[Table] As is clear from Table 2, the curing agent of the present invention has an excellent curing effect without impairing photographic properties when applied to a multilayer color film. In addition, reversal color processing (first development, water washing, reversal exposure, second development, water washing, bleaching, water washing, fixing, and water washing) was also performed on sample Nos. 9, 12, 13, 14, and 15, but sample No. Except for the occurrence of significant damage to the film surface in Sample No. 9, good films were maintained in all samples, and no particular problems were observed in the photographic properties. Example 3 In the same manner as in Example 2, a sample was prepared in which a hardening agent was added only to the gelatin protective layer, and a control sample was prepared in which no hardening agent was added. The hardness of each sample was measured in the same manner as in Example 1, and the results are shown in Table 3.

[Table] As is clear from Table 3, the curing agent of the present invention has a much faster dura mater progression than conventionally known curing agents.
Furthermore, it can be seen that it has an extremely excellent curing effect with virtually no posterior dura mater. Example 4 Gold and sulfur sensitizers were added to a silver chlorobromide emulsion containing 30% silver bromide, a second ripening was performed, a stabilizer, a coating aid, and a magenta coupler were added, and the emulsion was divided into eight parts. One part was left as is, and the other seven parts contained comparative curing agents (A), (B), (C), and curing agents of the present invention (1), (5), respectively.
After adding (9) and (10), the mixture was coated on polyethylene laminate paper and dried to prepare a control sample containing no hardening agent and 7 samples containing a hardening agent. Curing agent of the present invention (9) N,N',O-tris(4,6-dichloro-S
-triazin-2-yl)-1,3-diamino-
An aqueous solution obtained by partially hydrolyzing 2-propanol (Triazine Compound Example 13) in the same manner as in Production Example 2. Curing agent of the present invention (10) N,O-bis(4,6-dichloro-S-triazin-2-yl)-4-hydroxypiperidine (triazine compound example 29) was partially hydrolyzed in the same manner as in Production Example 2. Aqueous solution. Measurement of dura properties and 4-amino-3-methyl-
30 with a color developer based on N-ethyl-N-(β-methasulfonamidoethyl)aniline sulfate.
C. for 3 minutes and 30 seconds, followed by bleach-fixing, washing with water, and sensitometry. The results are shown in Table 4. Note that sensitometry was performed by measuring the reflection density through a green filter, and the sensitivity in the table is expressed as a relative value when the sensitivity of the control sample (sample No. 23) is set as 100.

[Table] As is clear from Table 4, the hardening agent of the present invention does not impair photographic properties, and in addition, compared to conventionally known similar hardening agents, the hardening agent progresses very quickly, and the posterior hardening is substantially reduced. It can be seen that it has an extremely excellent curing effect.

Claims (1)

[Claims] 1 At least one 4,6-dichloro-s-triazine bonded to the 2-position via a nitrogen atom in the molecular structure and 4,6-dichloro-s-triazine bonded to the 2-position via an oxygen atom in the molecular structure.
- A method for curing gelatin, which comprises reacting gelatin with a partial hydrolyzate of a compound having at least one of dichloro-s-triazine.