JPH0136092B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a gelatin curing method, and particularly to a gelatin curing method suitable for curing a gelatin film of a silver halide photographic light-sensitive material. Generally, photographic materials include, for example, a silver halide emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer,
It is made up of various layers such as a backing layer and an antihalation layer placed on a suitable support such as glass, paper, or synthetic resin film, and these various constituent layers are so-called gelatin films mainly composed of gelatin. It consists of 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-swellability, and weak mechanical strength, are fatal flaws in terms of the physical properties of the constituent layers of photographic light-sensitive materials. For this reason, various hardening agents have been applied to gelatin to cause crosslinking reactions with functional groups such as amino groups, carboxyl groups, and amide groups in gelatin molecules, thereby improving the physical properties of gelatin. Examples of such hardening agents include inorganic hardening agents made of polyvalent metal salts such as chromium alum, chromium trichloride, aluminum sulfate, and zirconium sulfate; aldehyde compounds such as formalin and glyoxal; 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, No. 48-13709, No. 13709-
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, JP-A-53-118486, JP-A-54-7320, etc., active ester compounds, U.S. Pat. No.
Epoxy compounds described in specification No. 3091537 and elsewhere, U.S. Patent Nos. 3321313 and 3543292
isoxazole compounds, halogencarboxaldehydes 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 action, and some have a long-term change in hardening action called "postdural", which occurs because the hardening reaction to gelatin is slow. additives, those that have an adverse effect on the properties of photographic light-sensitive materials (in particular, increased fog, decreased photosensitivity, changes in gradation, etc.), or those that coexist with other photographic additives (such as couplers in internal color emulsions). ), the curing action 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, and 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 during use and cause non-uniformity in photographic materials. 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 a desensitizing effect and an increase in fog, but also reduces the covering power. Alternatively, even if the hardness of the film is improved, the film becomes brittle, which tends to cause various drawbacks such as making it difficult to use in automatic processing machines. 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 into 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 may 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. It is an object of the present invention to cure gelatin, especially gelatin films of photographic light-sensitive materials, using a fast-acting hardening agent that eliminates almost all of the drawbacks of conventional hardening agents as described above and has no post-hardening film. The purpose of this study is to propose a gelatin hardening method suitable for use in gelatin. The object of the present invention is the following general formula (where m is 0 or 1, n is a positive integer, and X is (m
+n) valent aliphatic residue, aromatic residue, nitrogen atom,
R represents a 5- or 6-membered heterocyclic residue containing an oxygen atom or a sulfur atom, a 5-, 6- or 7-membered aliphatic residue, or a group to which these groups are connected; R represents a hydrogen atom or an organic residue; ) Dichloro-S
- Achieved by using a solution of a partial hydrolyzate of a triazine derivative with an alkali metal carbonate or an alkali hydroxide buffered with a phosphate and/or a borate as a hardening agent for gelatin. Specifically, in the general formula, 5- or 6-membered heterocyclic residues containing atoms (e.g. pyrrole ring, pyrrolidine ring, pyridine ring, pyrimidine ring,
furan ring, pyran ring, thiophene ring, etc.), 5, 6
Alternatively, it represents a 7-membered aliphatic residue or a group in which these groups are linked. 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, such as a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, an acyloxy group. , a heterocyclic group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a sulfo group, etc. May be replaced.
The organic residue represented by R is an aliphatic residue {for example, an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.), an alkenyl group (allyl group, butenyl group, etc.)}, an aromatic residue (for example, benzene ring, naphthalene ring, etc.), 5-, 6- or 7-membered aliphatic residue,
or acyl groups (e.g. acetyl, benzoyl,
naphthoyl, methanesulfonyl, P-tosyl, etc.)
represents. Each of these groups is a substituent listed for X,

[Formula] etc., and the substituent may be further substituted with the substituent listed for X. In addition, a part or all of R and , thiamorpholine ring, etc.Also, the alkali metal carbonate used in the present invention includes, for example, sodium hydrogen carbonate, sodium carbonate, or potassium carbonate, and the alkali hydroxide includes, for example, sodium hydroxide or Examples of phosphates include potassium hydroxide, tertiary phosphoric acid,
Examples of borates such as sodium, potassium or ammonium salts of diphosphoric acid or polyphosphoric acid include sodium, potassium or ammonium salts of metaboric acid or tetraboric acid. Here, the term "use as a hardening agent" refers to the reaction between the hardening agent and the gelatin to be hardened.
The reaction can be carried out by adding a curing agent to the coating solution and coating and drying, by adding a preliminarily reacted curing agent with gelatin to the coating solution and then coating and drying, or by coating and drying. 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. A method of immersing the agent in a solution containing the agent,
Furthermore, various known methods can be used, such as a method of immersing the film in a solution containing the curing agent before or during the development process. 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, is
It can be synthesized in good yield by a known general reaction. For example, when m is 0 in the above general formula, triethylamine,
Diisopropylethylamine, pyridine, 2,
using organic bases such as 4,6-collidine or Helvetica chimica acta.
Chimica Acta) Volume 33, pp. 1365-1369 (1950
), Journal of the American Chemical Society
American Chemical Society) Volume 78, No. 2989
(1951), U.S. Patent No. 2,824,823 and Journal of Heterocyclic Chemistry.
7, pp. 975-979 (1970) using an inorganic alkali such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. It can be synthesized from a compound having a hydroxyl group corresponding to . Furthermore, when m is a positive integer in the above general formula, the above-mentioned U.S. Pat.
3454551 and the Journal of Heterocyclic Chemistry.
Heterocyclic Chamistry) Volume 7, Nos. 975-979
(1970) from cyanuric chloride and a compound having the corresponding amino and hydroxyl groups, or from Helvetica Chimica acta (Helvetica Chimica acta).
Acta) Vol. 44, pp. 299-309 (1961), synthesize cyanuric chloride and a compound having a corresponding amino group and hydroxyl group by first reacting only the amino group. Then, the remaining hydroxyl moiety can be further reacted with cyanuric chloride to synthesize it in a manner similar to that described in the above-mentioned US Pat. No. 3,454,551. In the general formula, m is not particularly limited as long as m is 0 or a positive integer, and n is a positive integer. and/or a sulfur atom), or an (m+n)-valent group derived from an alicyclic group (especially a 5- or 6-membered ring) or an aromatic group (especially a benzene ring or a naphthalene ring). , R is a hydrogen atom or a lower alkyl group, and (m+n) is 2, 3 or 4, which is preferable in terms of achieving the objects and effects of the present invention. Furthermore, considering the synthetic aspects (ease of purification of intermediates, ease of partial hydrolysis, etc.), when m = 0 and n = 1, X is an alkyl group, especially a lower alkyl group, such as methyl or ethyl. , n-propyl, iso-propyl, etc. or 5- or 6-membered alicyclic groups are most preferred. Next, dichloro-
Although typical examples of S-triazine derivatives will be given, the raw materials for the curing agent used in the present invention are not limited thereby. Examples of triazine compounds The curing agent used in the present invention is these dichloro-S
- the triazine derivatives are combined with alkali metal carbonates such as sodium bicarbonate, sodium carbonate and/or
or partial hydrolysis treatment with an aqueous solution such as potassium carbonate, preferably at room temperature to 50°C, or an alkali hydroxide, such as sodium hydroxide and/or
Alternatively, partial hydrolysis treatment is performed with an aqueous solution such as potassium hydroxide, preferably at 0 to 5°C while maintaining the pH at 8 to 9 (in this case, the dichloro-S-triazine derivative may be directly treated with the alkali aqueous solution). (The dichloro-S-triazine derivative may be dissolved in an organic solvent, such as acetone or dioxane, and treated with the alkali aqueous solution.) After that, a phosphate, such as tertiary phosphoric acid, tertiary phosphoric acid, etc., is added to the treatment solution. By dissolving sodium, potassium and/or ammonium salts of diphosphoric acid and/or polyphosphoric acid, etc., and/or borates, such as sodium, potassium and/or ammonium salts of metaboric acid and/or tetraboric acid, etc. Obtainable. The obtained solution of the partial hydrolyzate may be used as it is or after diluting with water to an appropriate concentration and then dissolving the phosphate and/or borate, or it may be used as an aqueous solution containing an organic solvent. In such cases, the organic solvent may be distilled off and the phosphate and/or borate may be used as is or after diluting with water to an appropriate concentration, the phosphate and/or borate may be dissolved. Also, dichloro-S-
The amount of alkali metal carbonate used per mole of triazine derivative is (m+n)×1 to 6 moles,
The amount of alkali hydroxide is (m+n) x 1-2 mol and the amount of phosphate and/or borate is 0.25-
3 mol is preferred. When the hardening agent used in 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 per 1 g of dry weight of gelatin
~2.5×10 ⁻³ mol, preferably 5×10 ⁻⁶ ~2.5×
10 ^-4 mol. The timing of its addition may be at any stage of preparing the coating solution for forming the gelatin film, but for example, when it is added to a silver halide emulsion, it is generally added after the second heat formation of the silver halide emulsion. It is better. 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, including mechanically negative type, positive type, and diffusion transfer type photographic materials, there can be mentioned all types of photographic materials. 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 chlorobratinate, 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,
Addition of 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 util, and various other photographic additives. You can also do it. 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. Moreover, since there is very little 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 large amount 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 to apply photographic materials. Next, typical production examples of the curing agents used in the gelatin curing method of the present invention will be shown. Production example 1 Dissolve 37g of sodium hydrogen carbonate in 500ml of water,
While stirring at 40°C, a solution of 36 g of 2,4-dichloro-6-methoxy-S-triazine (triazine compound example 1) in 300 ml of acetone is added dropwise. After the dropwise addition, the mixture was stirred at the same temperature for 1 hour until the triazine compound was completely dissolved. Filter the solution, remove the acetone under reduced pressure, and remove 50 g of trisodium phosphate (12 hydrate).
and water to make a total solution of 1. Production Example 2 After reaction in exactly the same manner as Production Example 1, the solution was filtered,
Acetone is distilled off under reduced pressure, and 19 g of trisodium phosphate (12 hydrate), 28 g of disodium phosphate, and water are added to dissolve the total amount 1. Production example 3 Dissolve 34g of sodium hydrogen carbonate in 500ml of water,
While stirring at 40°C, 36 g of 2,4-dichloro-6-methoxy-S-triazine (triazine compound example 1) is added and suspended, and the mixture is stirred at the same temperature for 5 hours until the triazine compound is completely dissolved. The solution was filtered, and 27 g of sodium metaborate (tetrahydrate) and water were added to make a total solution of 1. Production example 4 Dissolve 35g of sodium hydrogen carbonate in 500ml of water,
While stirring at 40°C, a solution of 49.6 g of 2,4-dichloro-6-cyclohexyloxy-S-triazine (triazine compound example 13) in 300 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. The solution was filtered, the acetone removed under reduced pressure and trisodium phosphate (12
water salt) 38g, sodium metaborate (tetrahydrate) 14g
and water to make a total solution of 1. Since the curing agent used in the present invention synthesized as described above has a favorable curing reaction rate, the curing agent is added to a gelatin solution and the solution is mixed until a film is formed. It does not increase the viscosity of the gelatin solution. 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 the photographic material produced using the curing agent of the present invention is constant immediately after production. Therefore, when comparing a photosensitive material immediately after production with a photosensitive material that has been aged, there is no difference in the penetration rate of developer, etc. during processing, so there is almost no difference in apparent sensitivity or change in color balance. . Furthermore, photographic materials produced using the curing agent of the present invention can have film properties that can sufficiently withstand high-temperature rapid processing using strong processing liquids and automatic processing. 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 materials have been manufactured at higher speeds, and when extrusion coating is performed using a slide coater, for example, 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 solubility of curing agents in water is a very important advantage for the industry. 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. This does not reduce the effectiveness of the curing agent or cause the curing ability of the curing agent of the present invention to be lost. Moreover, it has an adverse effect on the properties of photographic light-sensitive materials (for example, increased fog, decreased photosensitivity, etc.)
does not affect The substances that can be hardened by the hardening agent used in 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 substances. Mixtures with hydrophilic polymeric substances can also be cured by the curing agent 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 thermal formation 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 10 parts, one of which was applied to a polyester base and dried to serve as a control sample, and the remaining 9 parts each of the following comparative curing agents (A), (B),
(C) and the curing agents (1), (2), (3), and (4) of the present invention were added, coated on a polyester base, and dried to prepare a sample. Comparative hardening agent (A) Mucochloric acid Comparative hardening agent (B) A curable solution obtained by partially hydrolyzing 2,4-dichloro-6-methoxy-S-triazine with an aqueous solution of twice the molar amount of sodium bicarbonate. Comparative Curing Agent (C) A curable solution obtained by partially hydrolyzing 2,4-dichloro-6-methoxy-S-triazine with an aqueous solution of 1.5 times the molar amount of trisodium phosphate (12 hydrate). 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 These Dural properties of the control sample 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°C and 80% relative humidity for 3 days were each immersed in a 3% aqueous solution of sodium carbonate at 25°C for 2 minutes. Immediately thereafter, the surface of the gelatin film was wiped off, and the film surface was scratched with a saphire needle having a tip with a radius of curvature of 1 mm, and the load at the time when the film surface began to be scratched was measured and expressed as the film surface strength. The results are shown in Table 1. In addition, [3 days heat treatment/1 day storage] in the table is the membrane surface strength ratio,
It was expressed as a measure of the difference in posterior dura mater properties.

[Table] As is clear from Table 1, the curing agent according to the present invention has an extremely excellent curing effect with very little post-hardening due to natural storage and heat treatment compared to conventionally known comparative curing agents. I understand. Incidentally, as a result of performing sensitometry on each sample stored for 7 days, it was found that none of the hardening agents impaired photographic properties such as sensitivity, gradation, fog, and maximum density. In addition, comparative curing agents (B), (C) and the curing agent of the present invention
After storing the curable solutions of (1), (2), (3), and (4) at room temperature for 3 months after production, samples were prepared in the same manner as above and the film surface strength was measured. Except for the fact that significant deterioration was observed in the sample prepared with agent (B), all of the measurement results were almost unchanged from the above-mentioned measurement results. 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 included 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 special public service 1977-
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, samples were prepared in which comparative curing agents (B), (C), and (D) and curing agents of the present invention (1), (2), (4), and (5) were added, respectively. Comparative Curing Agent (D) (a) Acetone solution of 2,4-dichloro-6-methoxy-S-triazine. (b) An aqueous sodium bicarbonate solution in an equimolar amount to the triazine derivative in (a). After adding (a), add (b). Curing agent of the present invention (5) An aqueous solution obtained by partially hydrolyzing 2,4-dichloro-6-ethoxy-S-triazine (Triazine Compound Example 2) in the same manner as in Production Example 3. The film surface strength of each sample was measured in the same manner as in Example 1. The results are shown in Table 2.

[Table] As is clear from Table 2, even when the curing agent of the present invention is applied to a multilayer color film, the hardening process progresses very quickly, and furthermore, it has an extremely excellent curing effect with virtually no post-hardening. I know what you're doing. For each sample stored for 7 days, 4-amino-3-methyl-N-
Color development was performed at 38°C for 3 minutes using a color developer containing ethyl-N-hydroxyethylaniline sulfate as the main ingredient, followed by bleaching, fixing, and washing in accordance with conventional methods, and sensitometry was performed. The curing agent of the invention did not impair photographic properties such as sensitivity, gradation, fog, and maximum color density. 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. 11, 15, 16, 17, and 18, but sample No. Except for the occurrence of significant damage to the film surface in No. 11, the film was well preserved in all the samples, and no particular problems were observed in the photographic properties. Example 3 A silver chlorobromide emulsion containing 30% silver bromide was subjected to a second ripening with the addition of gold and sulfur sensitizers, followed by the addition of stabilizers, coating aids, magenta couplers, and anti-fading agents. Divide into 6 parts, leave one part as is, and divide the other 5 parts into 6 parts.
Comparative curing agent (B), (C) and curing agent of the present invention
After adding (1), (2), and (3), they were coated on polyethylene laminate paper and dried to create a control sample without a hardening agent and five samples containing a hardening agent. The dura properties of each sample were measured in the same manner as shown in Example 1. The results are shown in Table 3.

【table】

[Table] As is clear from Table 3, the curing agent of the present invention exhibits an extremely excellent curing effect, with extremely rapid dura mater progression and virtually no post-dera mater, compared to conventionally known similar curing agents. It can be seen that it has. In addition, for each sample stored for 7 days, 4-amino-3-methyl-
A color developing solution whose main ingredient is N-ethyl-N-(β-methanesulfonamidoethyl) aniline sulfate.
Color development was carried out at 30°C for 3 minutes and 30 seconds, followed by bleaching, fixing, and washing with water.As a result of sensitometry, it was found that the curing agent of the present invention exhibited photographic characteristics such as sensitivity, gradation, fog, and maximum color density. There was no loss of characteristics. Example 4 Example 3 was carried out using the curing agents (20) and (21) of the present invention instead of the curing agents (1) and (2) of the present invention used in Example 3.
conducted a similar experiment. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1. General formula (where m is 0 or 1, n is a positive integer, and X is (m
+n) valent aliphatic residue, aromatic residue, nitrogen atom,
A 5- or 6-membered heterocyclic residue containing an oxygen atom or a sulfur atom, a 5-, 6- or 7-membered aliphatic residue, or a group to which these groups are connected; R represents a hydrogen atom or an organic residue; ) Dichloro-S-
A method for hardening gelatin, which comprises reacting gelatin with a solution of a partial hydrolyzate of a triazine derivative using an alkali metal carbonate or an alkali hydroxide buffered with a phosphate and/or a borate.