JPS6268867A - Hardening of gelatin - Google Patents

Abstract

PURPOSE:To accelerate the hardening of gelatin and to obtain a hardened gelatin causing little post-hardening, having high solubility in water and addable to a hydrophilic colloidal solution such as photographic emulsion without necessitating particular organic solvent, by using a specific compound as a hardener. CONSTITUTION:Gelatin is hardened by using at least one kind of the compound of formula I [R<1> and R<2> are alkyl, cycloalkyl, aralkyl, aryl alkenyl or heterocyclic group; R<1> and R<2> may together form a ring; R<3> is alkyl, cycloalkyl, aralkyl, aryl, alkenyl, heterocyclic group or group of formula II (R<4> and R<5> may be substituted with R<1> and R<2>); X is a group eliminable by the reaction of the compound of formula I with a nucleophilic reagent; the compound of formula I may form a salt with an acid] (e.g. the compound of formula III).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for curing gelatin using an improved curing agent, and particularly relates to a method for curing gelatin used in halogenated trowel photographic materials. .

(Prior Art) Layered gelatin is used as a binder in many photographic materials. In order to increase the water resistance and mechanical strength of the gelatin layer, methods of hardening gelatin using various compounds are conventionally known.

For example, aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Patent No. 3:2.r♂, 77
Reactive halogen-containing compounds described in No. j and others, U.S. Patent No. 3. Compounds having reactive ethylenically unsaturated bonds as described in Otomu No. 4Tza No. 6, Tokko Shouta No. 3363, and others, U.S. Patent No. 3.0/
7.21fO etc., the aziridine compounds described in U.S. Patent No. 3. O'? /, epoxy compounds described in No. 337, halogen carboxylaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane.

Additionally, chromium alum, zirconium sulfate, and the like are known as inorganic hardening agents.

However, when these known gelatin hardening agents are used in photographic light-sensitive materials, they either do not have a sufficient hardening effect or have a slow hardening reaction to gelatin, which causes a long-term change in the hardened layer called "postdural". , those that have an adverse effect on the properties of the photographic light-sensitive material (in particular, increased fog, decreased photosensitivity, etc.), or those that cause the curing effect to be lost due to the coexistence of other photographic additives, or other photographic additives (e.g. All of them had some drawbacks, such as those that reduced the effectiveness of color formers (for color photosensitive materials).

As a hardening agent that has a relatively fast hardening reaction to gelatin and causes less posterior dura, JP-A-Sho,! ; Compound having a dihydroquinoline skeleton described in No. 0-313jO, JP-A-3G-
Compounds having a phosphorus-halogen bond described in No. 113927, compounds having an N-nulfonyloxyimide group described in JP-A No. 32-93μ70, and furthermore, JP-A No. 33-2
Compounds containing two or more N-acyloxyimino groups in the molecule as described in No. 20 are known. Although these curing agents have the excellent property of rapidly curing and having very little so-called post-hardening, most of them are compounds with poor water solubility, and therefore they cause non-uniform curing in the photographic emulsion layer. It was easy to wake up. Furthermore, since a special organic solvent is required when added to a photographic emulsion or a photographic emulsion layer, problems such as uneven coating due to this organic solvent are likely to occur, and precautions such as explosion-proofing are required.

As curing agents that have a quick curing reaction with gelatin and are excellent in water solubility, N-carbamoylpyridinium salts described in JP-A-179-JL-45 and JP-A-Sho-5i-S-12J; Showa KA-110762
2-Fluphonyloxypyridinium salts described in the above are known.

These curing agents are highly water soluble, have a fast curing action, and are therefore characterized by less post-hardening. However, with these hardening agents, the hardening reaction of gelatin is fast, and the side reaction of decomposition by water is also fast. Therefore, the general production method ↑ that uses an aqueous solution of gelatin has the disadvantage that the effective use efficiency of the hardening agent is extremely low, and that a large amount of hardening agent must be used to obtain a gelatin film with the desired degree of hardening. Was.

Japanese Patent Publication No. 4t5i'-j / 4tj, Japanese Patent Publication No. 3/-J
No. 623 or Japanese Patent Publication No. 1071. ．． 2
It is generally believed that the hardening agents described in this issue undergo nucleophilic attack by carboxyl groups and amino groups of gelatin, react with them, and harden gelatin. When producing a gelatin film, 1. Usually, an aqueous gelatin solution is used, but since the water present at this time has a certain degree of nucleophilicity, it reacts with the hardening agent, decomposing it and rendering it ineffective. is unavoidable. This tendency is particularly noticeable for curing agents that exhibit rapid curing action. Therefore, in order to harden gelatin efficiently and quickly, it is necessary to develop a hardening agent that is more reactive with carboxyl groups and amine groups than with water in gelatin, that is, has good selectivity in its reaction with gelatin. is the key point. Curing agents such as N-carbamoylpyridinium salts and 2-nulfonyloxyviridinium salts have the disadvantage of extremely low efficiency of effective use of the curing agent, perhaps due to their low selectivity. There has been a strong desire to develop a hardening agent that is highly efficient in use, has a fast gelatin hardening reaction (and is highly water-soluble).

(Object of the Invention) The first object of the present invention is to provide a method for hardening gelatin using a novel gelatin hardening agent.

A second object of the present invention is to provide a gelatin hardening agent that has a fast hardening effect on gelatin and causes less post-hardening.

A third object of the present invention is to provide a gelatin hardening agent that is highly soluble in water and does not require a special organic solvent when added to a hydrophilic colloid solution such as a photographic emulsion.

Furthermore, the qth object of the present invention is to provide a gelatin hardening agent that reacts with high selectivity to reactive residues in gelatin and hardens gelatin efficiently.

(Structure of the Invention) As a result of extensive studies, the present inventors have discovered that the above object can be achieved by using a compound represented by the following general formula (1) as a hardening agent for gelatin.

General Formula (1) In the formula, R1 and R2 each represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, or a heterocyclic group. R and R2 may be combined with each other to form a ring. R3 is an alkyl group, a cycloalkyl group,
Aralkyl group, aryol group, alkenyl group, heterocyclic group,
Or it is the same as R1 and R2. These groups may be substituted and may be the same or different from each other.

X is a group that can be eliminated when the compound represented by the general formula (1) reacts with a nucleophile.

The compound represented by general formula (1) may form a salt with an acid.

To explain in more detail, R' and R2 are preferably linear or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.). , a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, a cyclohexyl group, etc.), a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 7 to 20 carbon atoms. 20 aralkyl groups (e.g. benzyl group, phenethyl group, etc.), carbon number 2~, 20 aryl groups (e.g. phenyl group, naphthyl group, etc.), carbon number 2
~coO alkenyl groups (eg, vinyl group, propenyl group, etc.), heterocyclic groups (eg, pyridyl group, etc.). R
', R2 may have a substituent, examples of which include a halogen atom, a nitro group, an alkoxy group having up to 20 carbon atoms,
Examples include an aryloxy group having t to 20 carbon atoms. The ring formed by combining R1 and R2 is preferably a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R3 preferably has 7 to 2 carbon atoms, which may be linear or branched.
00 alkyl group (e.g. methyl group, ethyl group, butyl group, coethylhexyl group, dodecyl group, etc.), carbon number 3
~． 20 cycloalkyl groups (e.g. cyclopropyl group, cyclohexyl group, etc.), carbon atoms 7 to . Aralkyl groups having 20 carbon atoms (eg, benzyl group, phenethyl group, etc.), aryl groups having 11 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), and alkenyl groups having 2 to 20 carbon atoms (eg, vinyl group).

propenyl group, etc.), heterocyclic groups (e.g. viridyl router) may have substituents, examples of which include halogen atoms,
Nitro group, alkoxy group with carbon number/-, 20, carbon number 6
~． 20 aryloxy groups, etc.

R and R preferably have a carbon number/~ which may be linear or branched.
20 alkyl groups (e.g. methyl group, ethyl group, butyl group, λ-ethylhexyl group, dodecyl group, etc.), aralkyl groups having 7 to 20 carbon atoms (e.g. benzyl group, phenethyl group, etc.), aryl groups having 6 to 20 carbon atoms group (e.g., phenyl group, naphthyl group, etc.), having 2 or more carbon atoms. It is a 2θ alkenyl group (eg, vinyl group, propenyl group, etc.).

Further, R1 and R2 or R4 and R5 may be combined with a nitrogen atom to form a valve ring, such as a pyrrolidine ring, a piperidine ring, a morpholine ring, etc.

X is a group that can be eliminated when the compound represented by the general formula (1) reacts with a nucleophilic -/θ- reagent, and preferred examples include a halogen atom (e.g., chlorine, bromine), a phthalimidyloxy group, a succinimidyloxy group, and a succinimide group. Zyloxy group, glutarimidyloxy group, azolyloxy group (e.g., l-benzotriazolyloxy group, etc.), ammonio group (e.g., l-pyridinio group, etc.), alkylnulfonyloxy group having 1 to 20 carbon atoms, carbon number Examples include the arylnulfonyloxy group of A-20. Moreover, X may be substituted.

The compound represented by the general formula (1) may form a salt with an acid, and an example of the acid is HC7! , ITB r.

HBF, , IIPF, , )Iα0. , H2SO,
, alkylnulfonic acid having 1 to 20 carbon atoms, carbon atN2
0f) Nurphonic acid (heteroaromatic ring-containing) is preferred.

Examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

compound l α Compound 2 α BF4 Compound 3 α compound q HC/! One no-fu compound j Compound 6 Compound 7 Number 1 BF4 compound α Next, examples of synthesis of these compounds will be shown.

Synthesis Example 1 (Synthesis of Compound 3) /-(N-cyclohexylcarbamoyl)pyrrolidine (
, 2oy) of /9,2-dichloroethane (700ml
) solution, trichloromethylentel chlorocarbonate (7
-) was added slowly at room temperature. After stirring as it was for 30 minutes, the temperature was raised to μOOC and further stirred for 2 hours. After distilling off the volatile components under reduced pressure, the residue was recrystallized with acetone to obtain Compound 3. (Yield 10./P) Chemical structure is nmr spectrum, ir7 vector, -7μ
Confirmed by elemental analysis.

Synthesis Example 2 (Synthesis of compound R) /, /, μ, 4L-tetramethylsemicarbazide (Ry
) and triphenylhonuphine (, z3.Ap) in acetonitrile (row) solution at room temperature with carbon tetrachloride (A, J
'*) was added and the mixture was stirred for 2 hours. After the acetonitrile was distilled off under reduced pressure, the mixture was extracted with ether C100d). After distilling off the ether under reduced pressure, the residue was distilled to obtain a compound. (Yield μ, coy) The chemical structure was confirmed by nmr spectrum, IR spectrum, and elemental analysis.

Other compounds can also be synthesized by the methods described above or by analogous methods.

When these compounds are applied as hardening agents to gelatin-containing photographic layers, undesirable phenomena such as fogging, deterioration of photographic properties such as desensitization, generation of nutin, and reaction with couplers contained in color photographic materials occur. Not observed. Further, the dura mater progresses extremely rapidly, reaching the final dura mater within a few days after application, and thereafter the phenomenon of increasing dura mater, that is, post-dura mater, is virtually not observed.

These compounds have excellent affinity for water.

No special organic solvent is required for addition, and therefore problems such as uneven coating due to this organic solvent will not occur. Also, there will be no need to pay attention to explosion-proofing, etc. Furthermore, these compounds have no special physiological effects and have low vapor pressure, so they have little adverse effect on the human body.

The amount of curing agent used in the present invention can be selected arbitrarily depending on the purpose. Usually 0 for dry gelatin
．． It can be used in proportions ranging from 7 to 20 cents by weight. Particular preference is given to using proportions ranging from 0.3 to IO weight percent.

The hardening agent of the present invention can also be effectively used as a hardening agent for partial hardening in a method of extending the chain length of gelatin by partial hardening, as described in JP-A No. 44-2324A. .

Furthermore, it can be used to harden such chain-extended gelatin.

The hardening agent of the present invention can be used in any photographic material using gelatin. For example, color negative film, color reversal film, color positive film, color photographic paper, color reversal photographic paper, color light-sensitive materials using color diffusion transfer method or scissors dye bleaching method, black and white film, X-ray film, film for plate making, black and white film. Black and white photosensitive materials such as photographic paper, aviation film, microfilm, facsimile film, phototypesetting film, photographic paper, and graph film.

Further, in this case, there is no particular limitation on the photographic layer using the hardening agent of the present invention, and it includes not only a halogenated complex emulsion layer but also non-photosensitive layers such as an undercoat layer, a back layer, a filter layer, an intermediate layer,
It can be used in any gelatin-containing photographic layer, such as an overcoat layer.

The curing agent of the present invention may be used alone, or a mixture of λ or more curing agents of the present invention may be used. Further, it may be used in combination with other curing agents known so far. Examples of known curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclontandione, binu(2-10 loethyl urea), and 2-hydroxy-t.
.

6-dichloro-/, 3.3 triazine, and more US Pat. No. 3.211.77! ; No. λ, No. 732°303, British Patent No. t? No. 79.723, ibid.

Compounds containing reactive halogens such as those described in No. 167.207, divinylnurphone, 3-7cetyl-1,3-diacryloylhexahydro-/13. j-
) Riryojin, et al. U.S. Patent No. 3,633,7/♂
No. 3,232,77゜3, British Patent No. Tata t1g
Compounds with reactive olefins such as those described in No. Otsu, N-hydroxymethylphthalimide, and other U.S. Patent No. 2,73.2.31A, 3g Otsu, /
N-methylol compounds described in US Pat. No. 6r, etc., incyanates described in US Pat. No. 3,103,1137, etc., US Pat. No. j, 0/7.

Aziridine compounds described in US Patent No. 2,72! ;, 291
No. 1, same, 7. ．． 72! Acid derivatives described in U.S. Patent No. 3,100゜7041, etc.; epoxy compounds, U.S. Patent No. 3.32/', 3/3, J, J
Inoxazole compounds described in No. 3.29.2.

Halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, the aforementioned dihydroquinoline compounds, compounds having a phosphorus-halogen bond, N-nulfonyloxyimide compounds, N-resyloxy imino compounds,
Examples include N-carbonyloxyimide compounds, cornulfonyloxyviridinium salts, N-carbamoylpyridinium salts, etc. described in 3333/1983. Or chrome light pan as a hardening agent for inorganic compounds.
Examples include zirconium sulfate. Also, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts and methylol derivatives of hydantoin.

It may be used in combination with a primary aliphatic ditroalcohol, a mesyloxyethylnulfonyl compound, a chloroethylnulfonyl compound, or the like. When using the curing agent of the present invention in combination with another curing agent 1. The curing agent of the present invention can be used at any ratio depending on the purpose and effect, but the curing agent of the present invention should be used in combination with 30 mol. It is preferable that

A compound that accelerates the hardening of gelatin can also be used together with the hardening agent of the present invention.

For example, a polymer containing a nurfin group described in JP-A-36-≠1III is used as a hardening accelerator in the system of the curing agent of the present invention and a vinyl nurphone-based curing agent.

In the manufacturing process, gelatin to which the hardening agent of the present invention is applied is subjected to so-called alkali-treated (lime-treated) gelatin immersed in an alkaline bath, acid-treated gelatin immersed in an acid bath, or both treatments before gelatin extraction. Either double-soaked gelatin or enzyme-treated gelatin may be used. Furthermore, the hardening agent can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

Gelatin to which the hardening agent of the present invention is applied may optionally contain colloidal albumin, casein, cellulone derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate, starch derivative dextran, and synthetic hydrophilic It can be replaced with a sexual colloid, such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives/partial hydrolysates thereof, and may also be replaced with so-called gelatin derivatives. .

When the curing agent of the present invention is used in a photographic light-sensitive material, the photographic emulsion layer and other layers may also contain synthetic polymer compounds, such as latex-like water-dispersed vinyl compound polymers, which particularly increase the dimensional stability of the photographic material. These compounds may be contained alone or in combination, or in combination with a hydrophilic water-permeable colloid.

When the gelatin curing agent of the present invention is used in a photographic material, it can be used together with a matting agent. The matting agent is preferably a fine particle of a water-insoluble organic or inorganic compound with an average particle diameter of 0.2 to 10 μ, particularly preferably 0.3 μ to jμ.

The gelatin hardener of the present invention can be used in combination with various color couplers.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Di 5closures.

(hereinafter abbreviated as RD) i7ata3 (December, i7r) V
Section I I-D and same/za 7/7C1 year//month)
Described in the patent cited in .

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler in which the coupling-coco active position is substituted with a leaving group can reduce the amount of coated buttons and provide higher sensitivity than a two-equivalent color coupler in which the coupling-coco active position is substituted with a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

Typical examples of yellow couplers that can be used with the gelatin hardener of the present invention include oil-protected acylacetamide couplers.

In the present invention, it is preferable to use a two-equivalent yellow coupler, and representative examples include an oxygen atom elimination type yellow coupler or a nitrogen atom elimination type yellow coupler. α-pivaloyl acetanilide couplers have excellent color fastness, especially light fastness, while α-benzoyl acetanilide couplers provide high color density.

Magenta couplers that can be used with the gelatin hardener of the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue of the coloring dye and the coloring density. As the leaving group for the two-equivalent j-pyrazolone coupler, a ryolylthio group is particularly preferred. Also European Patent No. 73.1.31. The 3-pyrazolone coupler having a ballast group described in the above issue provides high color density. As the pyrazolo ryozole coupler, pyrazolobenzimidazoles, preferably pyrazolo(j,/-c)
(l12.<<) Triazoles, pyrazolotetrazoles and pyrazolopyrazoles. Imidazo (/, 2-b) pyrazoles are preferred from the viewpoint of low yellow side absorption of the color dye and light fastness, and pyrazolo (/, t-b) (/, 2.4 () triazoles are particularly preferred). ..

Cyan couplers that can be used with the gelatin hardener of the present invention include oil-protected naphthol-based and phenolic couplers;
Typical examples include naphthol couplers described in No. 717,223, preferably two-equivalent naphthol couplers of the oxygen atom separation type. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler having 2.3-
These include diacylamino-substituted phenolic couplers and phenolic couplers having a phenylureido group at the λ-position and an acylamino group at the j-position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility.

231 The gelatin hardener of the present invention may be used in combination with a coupler that releases a development inhibitor (so-called DIR coupler) during development.

Examples of DIR couplers include those that release heterocyclic mercapto type development inhibitors; those that release benzotriazole derivatives as development inhibitors; colorless DIR couplers; and nitrogen-containing heterocyclic development inhibitors with decomposition of methylol after separation. Those that release the development inhibitor with an intramolecular nucleophilic reaction after elimination; Those that release the development inhibitor by electron transfer through a conjugated system after elimination; The development inhibitory ability is lost in the developer. those that release active diffusible development inhibitors;
Examples include those that release a reactive compound and generate a development inhibitor or deactivate the development inhibitor through a reaction in the film during development. A compound that releases a fogging agent or a development accelerator or a precursor thereof through a coupling reaction or redox reaction with an oxidant can be used in combination.

When the present invention is used in a light-sensitive material, a compound that releases an electron-donating compound or its precursor through a coupling reaction or redox reaction with an oxidized developing agent can be used in combination.

When using various couplers in combination in the present invention, two or more couplers can be used together in the same photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in combination with different couplers. It is also possible to introduce more than one layer.

When the present invention is used in a silver halide photosensitive material, the silver halide emulsion is usually a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide alone or a mixture thereof) solution mixed with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as Typical silver halides produced in this manner include iron chloride, silver bromide, and mixed silver halides such as chlorobromide, chloroiobromide, and silver iodobromide. The average particle size of the halogenated coin particles (in the case of spherical or near-spherical particles, the particle diameter is the particle size; in the case of cubic particles, the principal is the particle size, and the average is based on the projected area) is λμ or less and 0. It is preferably 1μ or more, and particularly preferably /μ or less o and isμ or more. The particle size distribution may be narrow or wide. ±4 of the average particle size in terms of particle number or weight (0% or more of total particles within 01, especially
A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which the grain size distribution is at least % can be used in the present invention.

The shape of the silver halide grains that can be used in the present invention may be regular crystals such as cubic, octahedral, dodecahedral, and tetradecahedral, or spherical. It may have an irregular crystal form such as, etc., or it may have a composite form of these crystal forms.

Tabular grains may also be used, especially those with a length/thickness ratio of 3.
In particular, the tabular grains of g or more are 3 g of the total projected area of the grains.
An emulsion containing 0% or more may also be used.

The halide emulsion to which the present invention can be applied can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); reduction sensitization using metal compounds (e.g., total complex salts, Pt,
■r.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table, such as Pd, Rh, and Fe, can be used alone or in combination.

Photographic emulsions to which the present invention can be applied are spectrally sensitized with photographic sensitizing dyes. Dyes that can be used include cyanine dyes, merocyanif dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicillin dyes, nutyryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine color 8 and cotter and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

The photographic emulsion to which the present invention can be applied may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles (preferably !-nitrobenzimidazoles), nitroindazoles, benzotriazoles (preferably 3-methylbenzotriazoles) ), trizoles, etc.; Mercapto compounds 1, such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptooxadiazoles, mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles ( %/-phenyl-j-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thiocarbonyl compounds, such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially q-hydroxy -Otsu-Methyl-(7S3
．． 3a, 7) Antifoggants such as tetraazaindene), pentaazaindene; henzenethionurphonic acids, benzenenurphinic acid, benzenenurphonamides: purines such as adenine, etc.; Many compounds known as stabilizers can be added.

The photosensitive material produced using the present invention can be used as a coating aid, to prevent static electricity, to improve stickiness, to emulsify and disperse, to prevent adhesion, and to improve photographic properties (for example, to accelerate development, increase contrast, and sensitize). It may also contain a surfactant.

As a surfactant, for example, saponin (Nuteroid type)
, alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or Nonionic surfactants such as amides, polyethylene oxide adducts of silicone), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl carboxylates, alkylbenzene nulphonates, Alkylnaphthalene nulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, null cat succinates, nullhoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants such as esters containing acidic groups such as cal-oxy groups, nurho groups, honuho groups, entel sulfate groups, and entel phosphate groups can be used.

More preferably used surfactants include fluorine-containing surfactants. Examples of fluorine-containing surfactants include Japanese Patent Publication Sho≠Doichi μ3/30 and JA-
Compounds described in 4uμ // publication and 47-7303 publication can be preferably used.

In addition to the above-mentioned additives, the light-sensitive material produced using the present invention further contains various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or their precursors, lubricants, mordants, Matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure/Volume 7A, T-Erm/7A4L3 (July 1971).
．． February) Oyobido/l? Volume 7 completed I'am/J'7#
It is written in (/ri7chi//month).

There are no particular limitations on the development of the photosensitive material produced using the present invention, and known color development and black-and-white development can be used.

Regarding the development process, reference may be made to the description in the aforementioned Research Dinuklosure Volume 776 Item/7Ag 3 (/7F/, February).

The present invention will be further explained below with reference to Examples.

However, the present invention is not limited to these examples.

Example / Compound 3 according to the invention, compound 3 and as a comparative example %
JP-A-5i-t5i't, 2. No. (Exemplary Compound 76)
K disclosed, Irohikaku compound (1> or U.S. Patent 3
, 1s11.2. Comparative compounds (If) disclosed in No. 6 (Example ■) were added to 7 gelatin aqueous solutions in the proportions shown in Table 1, and a dry film thickness of about gμm was formed on a cellulose triacetate support. Apply it evenly so that
It was further dried to create gelatin films (A) to (G). In addition, gelatin films containing no hardening agents (If
) was also created as a control. These samples
230C1-3μm Placed in an environment with humidity of SO, 1 hour after application, 7 days,
After 3 and 7 days, a part of each sample was taken out and the number of crosslinks (cross 1 day) was determined by the following method.
coefficient) δ (1 of gelatin before crosslinking)
The number of crosslinking units per average molecular weight was determined.

(How to determine the number of crosslinks δ) Each gelatin film was separated from the support, and its weight and Ml were measured. The sol content was extracted from these gelatin films with warm water, and the amount of gelatin, Ml, was determined by the microbiulet method. The sol fraction, S, was determined from these nodules according to the following formula.

M.

From the calculated value of S, human
tionand Polymers”, Pergam
Published by onPres s (60 years) / Ell-13
δ was calculated according to the following formula described on page 1.

Table 1 shows δ of gelatin films (A) to (H) at each aging time.

Comparative compound (T) Comparative compound (II) CH2-CH8O2CH20CH2SO2CH-C11
2 As can be seen from the results in Table 1, gelatin films (A) to (D) using Compound 3 or glue of the present invention all have a fast curing action (the curing reaction is completed in about λ hours after application). After that, δ does not change.

Comparative compound N) was similar to Compound 3 and 3 in terms of speed of hardening action, but was used in the same amount as Compound 3 and 3, probably due to poor selectivity between the reactive residues in gelatin and water. When comparing the systems (gelatin films (A), (C) and (E) or gelatin films (B), (D) and (F)), δ is small and the efficiency of effective use as a hardening agent is low.

In addition, it can be seen that the curing effect of the comparative compound (It) was slow (and δ increased even after 3 days (posterior dura).

From the above results, it is clear that Compounds 3 and 7 according to the present invention have a fast curing effect and are curing agents with excellent usage efficiency.

Example Compound 3 according to the present invention and comparative compound (II) shown in Table 2 were added to a high-speed negative photographic emulsion containing gelatin at 7.20 F and silver iodobromide at 7.20 F per emulsion prepared according to a conventional method. A sample was prepared by adding the following ingredients, uniformly coating the base coated cellulose triacetate support to a dry film thickness of 70 μm, and drying.

Next, each sample was left to stand at room temperature for 7 days, and then the degree of swelling Q, which is expressed by the following formula, was measured in 2j'C water.

In addition, the sample was immersed in water, and a needle with a corundum tipped with a radius Q and pw was pressed onto the sample surface for 7 seconds: l, , j
0-2009 because it moves parallel on the membrane surface at the speed of am.
The load on the needle that caused damage to the membrane surface of the sample was determined by continuously changing the load within the range of .

Furthermore, the obtained film sample was wedge exposed and D-
Developed with 76 developer for 20'C, f minutes, fixed, washed with water,
After drying, sensitometry was performed to determine sensitivity and fog. The obtained results are summarized in the second group.

As is clear from Table 2, the compounds of the present invention have film strengths sufficient for practical use and do not impair photographic properties.

-μO- -μl- Example 3 A silver iodobromide emulsion containing 3.0 molt of silver iodide was prepared and subjected to post-heating in the presence of sodium thiosulfate and gold salt to obtain the highest sensitivity. A high-sensitivity negative emulsion was obtained.

This emulsion contains /-(2', μ', A'-trichlorophenyl)-3-(j'-(2''', μ''''-jit
-Amylphenoxy-rcetamidons-endamide]-j-
Pyrazolone was dissolved in the dibutyl tucrate and tricresyl phonufate mixture, sorbicun monolaurate,
The compound 3 of the present invention was mixed with a coupler emulsion obtained by emulsifying and dispersing funnel oil and sodium dodecylbenzeneulfonate in an o/vy type in a gelatin solution as a dispersing emulsifier.
An experimental color film of a single magenta layer was coated and dried to a dry film thickness of about 10 μm on a base coated triacetic acid Cellulone Baine with g, o) (,20 mmol) per 100 y of dry gelatin. Obtained.

This experimental color film was wedge exposed.

-μ2- A color development process using t-amino-3-methyl-N-ethyl-β-hydroxyethianiline senuxulfate monohydrate as the main agent was carried out, and the color development characteristics were examined by sensitometry.

As a result, it was found that the compound of the present invention did not impair the coloring performance of the coupler and did not generate color nutin.

Patent applicant: Fuji Photo Film Co., Ltd. J-

Claims (1)

[Claims] A gelatin curing method characterized by using at least one compound represented by the following general formula (1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R ^1 and R^2 are respectively an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group,
Or represents a heterocyclic group. R^1 and R^2 may be combined with each other to form a ring. R^3 represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a heterocyclic group, or a ▲ group that has a numerical formula, chemical formula, table, etc. R^
4. The definition of R^5 is the same as R^1R^2. These groups may be substituted and may be the same or different from each other. X is a group that can be eliminated when the compound represented by the general formula (1) reacts with a nucleophile. The compound represented by general formula (1) may form a salt with an acid.