JP3521376B2 - Silver halide photographic light-sensitive material and image forming method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an improved silver halide photographic light-sensitive material for printing plate making.

[0002]

2. Description of the Related Art In recent years, in the printing plate making scanner market, a screening method for forming an image with halftone dots smaller than the conventional one, such as high definition and FM screening, has begun to spread. For such a screening method, an ultra-high contrast type photosensitive material that is easy to apply small-dot density is suitable.

In a silver halide photographic light-sensitive material for printing plate making (hereinafter, also simply referred to as a light-sensitive material), as a photographic technique capable of reproducing a super-high contrast image, for example, US Pat.
A light-sensitive material containing a hydrazine derivative disclosed in JP-A-9,929 or a light-sensitive material containing a nucleation accelerator as disclosed in JP-A-4-98239 is known.

On the other hand, the photosensitive material is easily scratched by its handling or by various kinds of conveying devices. Even in the case of the photosensitive material for printing plate making, it is scratched by friction with the conveying roller of the scanner exposure device or contact between the photosensitive materials. Blackening easily occurs.

A scratch defect of the film not only damages the photosensitive material but also significantly deteriorates the quality of the finished document. Therefore, it is strongly desired to improve scratch resistance.

In a scanner / exposure machine for a photosensitive material for printing plate making, the photosensitive material is generally set and conveyed in a roll form. At this time, if the curl of the photosensitive material is too strong, conveyance failure occurs. Further, it is desirable that the film after the development processing has less curl so that it can be easily handled in the next step,
It is important to suppress curling of the photosensitive material before and after the exposure process.

It has been well known in the past to add a softening agent (eg, polymer latex) to the gelatin layer to reduce the Young's modulus of the gelatin layer in order to prevent the curl due to expansion and contraction of the gelatin layer. Further, a softener or a plasticizer is used for the purpose of preventing cracking of the film or the above-mentioned scratches, and many techniques have been disclosed.

However, the recent rapid processing of the light-sensitive material further increases the film transport speed, so that the physical properties of the film by the conventional techniques are not sufficient, and further improvement techniques are needed. Further, physical properties of a film film which does not deteriorate the drying speed in rapid processing have been desired.

[0009]

Therefore, an object of the present invention is to provide a film with excellent scratch resistance or crack resistance.
Another object of the present invention is to provide a silver halide photographic light-sensitive material which has little curl before and after processing and is easy to use. Furthermore, it is to provide a silver halide photographic light-sensitive material having a high drying rate in rapid processing.

[0010]

The objects of the present invention have been achieved by the following constitutions.

(1) In a silver halide photographic light-sensitive material having a layer structure of 3 to 10 layers on a support, at least one layer is a light-sensitive silver halide emulsion layer and at least one layer is a hydrophilic colloid layer. And the photosensitive silver halide emulsion layer has a spectral sensitization maximum at 600 to 900 nm,
And, of content upon which coated through the light-sensitive silver halide emulsion layer and / or the hydrophilic colloid layer, a composite latex comprising inorganic particles and a hydrophobic polymer in the coating solution
The pH of the coating solution is 4.0 to 6.9,
, The total coating amount of gelatin on the side of the photosensitive silver halide emulsion layer
Is 1.0 to 3.6 g / m ² , and the hydrophilic co-
The photosensitivity of at least one latex in the Lloyd layer
Combined with total gelatin coating amount (A) on silver halide emulsion layer side
A silver halide photographic light-sensitive material characterized in that the total coating amount (B) of latex contains an amount satisfying the following formula [1] . Formula [1] 1.0 ≦ (A) / (B) ≦ 17.5

(2) At least in the hydrophilic colloid layer
Also described in 1 above , characterized in that it also contains one kind of slip agent.
The listed silver halide photographic light-sensitive material.

(3) At least in the hydrophilic colloid layer
On characterized by also containing one water-soluble polymer
The silver halide photographic light-sensitive material as described in 1 or 2 above .

(4) At least in the hydrophilic colloid layer
1 to 1 above, which also contains one kind of matting agent
The silver halide photographic light-sensitive material as described in any one of 3 above .

(5) The method according to any one of 1 to 4 above
Light-sensitive silver halide emulsion layer of silver halide photographic light-sensitive material
A high contrast amount of hydrazide in the middle and / or hydrophilic colloid layer
A silver halide photographic light-sensitive material characterized by containing a silver derivative .

(6) The method according to any one of 1 to 5 above
Light-sensitive silver halide emulsion layer of silver halide photographic light-sensitive material
A high contrast amount of hydrazide in the middle and / or hydrophilic colloid layer
Release the development inhibitor by being oxidized.
Ururedox DIR compound
Silver halide photographic light-sensitive material that.

(7) The method according to any one of 1 to 6 above.
After exposing the silver halide photographic light-sensitive material, the pH of the developer is 9.
By processing at 5 to 11.0, gamma of 10 to 30
A silver halide copy characterized by forming a tough image
Image forming method of true photosensitive material.

[0018]

[0019]

[0020]

[0021]

The present invention will be described in detail below.

The silver halide photographic light-sensitive material of the present invention has a layer structure of 3 to 10 layers on a support.

The term "layer" as used herein refers to a photosensitive silver halide emulsion layer, a non-photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, a dye layer and other hydrophilic layers. It is a light-sensitive material composed of 10 to 10 layers, preferably 3 to 8 layers, and more preferably 3 to 6 layers.

At least one layer is a photosensitive silver halide emulsion layer and at least another layer is a hydrophilic colloid layer.

The light-sensitive silver halide emulsion layer according to the present invention has a spectral sensitization maximum in the range of 600 to 900 nm, and the inorganic layer in the light-sensitive silver halide emulsion layer and / or the hydrophilic colloid layer is inorganic. It contains a composite latex composed of particles and a hydrophobic polymer.

The photosensitive silver halide emulsion layer having a spectral sensitization maximum at a wavelength of 600 to 900 nm means an emulsion having a spectral sensitization maximum at a wavelength of 600 to 900 nm by a sensitizing dye. The preferable maximum value of sensitization is 610 to 8
Within 90 nm.

The spectral sensitizing dye having a spectral sensitization maximum at 600 to 900 nm used in the present invention is not particularly limited, but the following general formula [Ia] or [Ib] is used.
A dye selected from compounds represented by

[0029]

[Chemical 1]

In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a benzothiazole ring or naphtho. Thiazole ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring,
Examples thereof include a quinoline ring, a 3,3-dialkylindolenine ring, a benzimidazole nucleus and a pyridine ring.

These heterocycles may be substituted with a lower alkyl group, an alkoxy group, a hydroxyl group, an aryl group, an alkoxycarbonyl group or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, -N <W.
Represents ₁ W ₂ . Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are connected to each other. It is also possible to form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ may be connected to each other to form a 5- or 6-membered ring. X ₁₁ ^- and X ₂₁ ^- is an anion. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂
Represents 0 or 1.

Specific examples of the above-mentioned cationic di- or tricarbocyanine dyes used in the present invention are shown below, but the present invention is not limited thereto.

[0036]

[Chemical 2]

[0037]

[Chemical 3]

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

As the spectral sensitizing dye having a spectral sensitization maximum in the range of 600 to 900 nm used in the present invention, in addition to the above, the following general formulas [II], [III], [IV], [V] and [VI] are used.
A dye selected from compounds represented by

[0042]

[Chemical 7]

In the formula, X is a sulfur atom or a selenium atom, and at least two of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an organic group having a water-soluble group. However, both R ₃ and R ₄ do not represent this. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ that do not represent the above organic group having a water-soluble group are a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl. Represents a group. Z represents a condensed ring, R ₆ or R ₇ are the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group,
Substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, aryl group, substituted aryl group, acyl group, substituted Acyl group, acyloxy group,
It represents a substituted acyloxy group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an alkylsulfonyl group, a substituted alkylsulfonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, and a cyano group.

[0044]

[Chemical 8]

In the formula, Y is a sulfur atom or a selenium atom, and at least two of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent an organic group having a water-soluble group (provided that R ₁₄ , R
_{The 15s} do not represent this together. ), R _{11 to} R ₁₆ which do not represent the organic group having a water-soluble group represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, or a substituted aryl group, and R ₁₇ and R ₁₈ is the same or different and is the same as defined for R ₆ and R _{7 in} the above general formula [II] or R together with R _17
18 represents the atoms necessary to together form a carbocyclic ring system. The ring system may carry one or more groups, which may be the same or different, selected from the groups indicated for R ₆ and R ₇ .

[0046]

[Chemical 9]

In the formula, Y ₁ and Y ₂ each represent a non-metal atomic group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring. The heterocycle of is a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group,
It may be substituted with an alkoxycarbonyl group or a halogen atom.

R ₂₁ and R ₂₂ are each a lower alkyl group,
It represents an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R ₂₃ is a methyl group, an ethyl group,
Represents a propyl group. X ₁ ^- represents an anion. n ₁ , n
₂ represents 1 or 2. m ₁ represents 1 or 0, and in the case of an inner salt, m ₁ represents 0.

[0049]

[Chemical 10]

In the formula, R ₃₁ and R ₃₂ each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or an allyl group, and at least one of R ₃₁ and R ₃₂ is an alkyl group containing a sulfo group or It represents an alkyl group containing a carboxyl group. R ₃₃ and R ₃₄ each represent an alkyl group. Z ₁ is 5
Represents a nonmetallic atomic group necessary for completing a 6-membered or 6-membered nitrogen-containing heterocyclic nucleus.

[0051]

[Chemical 11]

In the formula, Y ¹ is —S— or —Se— and L ¹ , L ² , L ³ , L ⁴ and L ⁵ each represent an optionally substituted methine group. A is ^{-N (R 3) -, -} O -, - S- and represents, when A is -O-, B is -N (R ⁴⁾ - represents a. A
When, B is -N (R ⁴⁾ - - but -N (R ^3), - represents a S- or -O-.

R ¹ , R ² , R ³ and R ⁴ each represent an optionally substituted alkyl group or an optionally substituted aryl group, and R 1
⁵ represents an alkyl group having 1 to 4 carbon atoms. Where R ¹ ,
At least two of R ² , R ³ and R ⁴ are substituted with an acid or acid salt. n represents 0, 1 or 2, and X ⁻ represents a counter ion.

Specific examples of the spectral sensitizing dyes represented by the above general formulas [II] to [VI] are shown below.

[0055]

[Chemical 12]

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

The sensitizing dye according to the present invention is preferably 1 mg to 2 g, and preferably 3.5 m per mol of silver halide.
It is contained in the silver halide emulsion in the range of g to 1 g.

The sensitizing dye of the present invention can be directly dispersed in a silver halide emulsion. Alternatively, they may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The time of addition may be any time during the production process of the silver halide photographic light-sensitive material, but preferably any time from physical ripening to immediately before coating.

The sensitizing dyes of the present invention may be used alone or in combination of two or more kinds. Also, sensitizing dyes other than those of the present invention can be used in combination. When other sensitizing dyes are used in combination, the total amount is preferably the above content.

The photosensitive silver halide emulsion layer and / or the hydrophilic colloid layer according to the present invention contains a composite latex composed of inorganic particles and a hydrophobic polymer.

The composite latex composed of inorganic particles and a hydrophobic polymer will be described below.

Examples of the inorganic particles used together with the hydrophobic polymer include metal oxides, nitrides, sulfides and the like, but metal oxides are preferable. As the metal oxide, Na, K, Ca, Ba, Al, Zn, Fe, Cu, T
i, Sn, In, W, Y, Sb, Mn, Ga, V, N
b, Tu, Ag, Bi, B, Si, Mo, Ce, Cd,
Single or composite oxide particles of metals such as Mg, Be and Pb are preferable, and particularly preferable are Y, Sn, Ti, Al,
Single or complex oxide particles of V, Sb, In, Mn, Ce, B and Si are particularly preferable from the viewpoint of compatibility with the emulsion.

Such metal oxides can be preferably used in either crystalline or amorphous form, and particularly amorphous metal oxide particles are preferably used. The average particle size of the metal oxide is preferably 0.5 to 3000 nm and 3 to 500 nm.
Is particularly preferable. Such a metal oxide is preferably dispersed in water and / or a water-soluble solvent.

The amount of the metal oxide added is preferably 1 to 2000% by weight, more preferably 30 to 1000% by weight, based on the hydrophobic polymer. Examples of preferable metal oxides are shown below.

SO-1 SiO ₂ SO-2 TiO ₂ SO-3 ZnO SO-4 SnO ₂ SO-5 MgO SO-6 MnO ₂ SO-7 Fe ₂ O ₃ SO-8 ZnSiO ₄ SO-9 Al ₂ O ₃ SO-10 BeSiO ₄ SO-11 Al ₂ SiO ₅ SO-12 ZrSiO ₄ SO-13 CaWO ₄ SO-14 CaSiO ₃ SO-15 InO ₂ SO-16 SnSbO ₂ SO-17 Sb ₂ O ₅ SO-18 Nb ₂ O ₅ SO-19 Y ₂ O ₃ SO-20 CeO ₂ SO-21 Sb ₂ O ₃ SO-22 Na ₂ O In the composite latex of the present invention, the hydrophobic monomer forming the hydrophobic polymer is, for example, acrylic. Acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diester , A fumaric acid diester, an allyl compound, a vinyl ether, a vinyl ketone, a vinyl heterocyclic compound, a glycidyl ester, an unsaturated nitrile, and a hydrophobic single compound of a combination of two or more kinds selected from various unsaturated acids. Mention may be made of the quantity. The hydrophobic monomer forming the hydrophobic polymer of the present invention is preferably acrylic acid ester and / or
Or methacrylic acid esters and styrenes,
It is particularly preferable that the ester group has 6 or more carbon atoms.

At least 1.0 to 20 wt% of a hydrophobic monomer having a glycidyl group is added to these hydrophobic monomers,
It is preferable to use 20 to 100 wt%.

The hydrophobic polymer forming the composite latex of the present invention is preferably copolymerized with a hydrophilic monomer in addition to the hydrophobic monomer. Examples of such a hydrophilic monomer include acrylic monomers. Carboxyl group-containing monomers such as acids and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate, alkylene oxide-containing monomers, acrylamides, methacrylamides, sulfonic acid group monomers, amino group-containing monomers Although the body and the like can be preferably used, a hydroxyl group-containing monomer, a carboxyl group-containing monomer,
It is particularly preferable to include an amide group-containing monomer and a sulfone group-containing monomer.

Since such a hydrophilic monomer is dissolved in water when added in a large amount, its content is preferably 0.1 to 30 wt%, particularly preferably 1.0 to 20 w.
t%.

The composite latex of the present invention can be crosslinked with, for example, a carboxyl group, a glycidyl group, an amino group, an amide group or an N-methylol group by selecting the kind of the above-mentioned hydrophobic monomer and / or hydrophilic monomer. A composite latex having a crosslinkable group can be obtained by using a hydrophobic monomer having a group.

The composite latex of the present invention may contain at least two copolymerizable ethylenically unsaturated monomers. Examples of such a monomer include those having two vinyl groups such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and N, N-methylenebisacrylamide, trivinylcyclohexane. , Those having three vinyl groups such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate, and those having four vinyl groups such as pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate. However, it is not particularly limited thereto.

The average particle size of the composite latex of the present invention is particularly preferably 0.01 to 0.8 μm in terms of weight average particle size,
Any of those having a thickness of 0.005 to 3.0 μm can be preferably used.

Examples of the method for polymerizing the composite latex of the present invention include emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method and radiation polymerization method.

In solution polymerization, a mixture of monomers having a suitable concentration in a solvent (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) is added in the presence of an initiator to about 10% by weight. It can be obtained by carrying out the polymerization at a temperature of 200 ° C., preferably 30 to 120 ° C. for about 0.5 to 48 hours, preferably 2 to 20 hours.

Any initiator may be used as long as it is soluble in the polymerization solvent, for example, benzoyl peroxide, azobisisobutyronitrile (AIBN), an organic solvent initiator such as ditertiary butyl peroxide, ammonium persulfate ( APS), potassium persulfate, water-soluble initiators such as 2,2'-azobis- (2-amidinopropane) -hydrochloride, and a redox system in which these are combined with a reducing agent such as Fe ²⁺ salt or sodium hydrogen sulfite. A polymerization initiator etc. can be mentioned.

Any solvent may be used as long as it can dissolve a mixture of monomers, and for example, water, methanol, ethanol,
Examples thereof include dimethyl sulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more of these. After completion of the polymerization, the unreacted mixture can be separated and removed by pouring the reaction mixture into a medium in which the produced copolymer is not dissolved, allowing the product to settle, and then drying.

In the emulsion polymerization method, water is used as the dispersion medium, and 10 to 50% by weight of the monomer relative to water and 0.
About 30 to 100 ° C., preferably 60 to 90 ° C. using 05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant.
It is obtained by polymerizing under stirring for 3 to 8 hours.
The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

As the initiator, a water-soluble peroxide (eg potassium persulfate, ammonium persulfate etc.), a water-soluble azo compound (eg 2,2′-azobis- (2-amidinopropane) -hydrochloride etc.) or a combination thereof ^Examples thereof include a redox type polymerization initiator in which a reducing agent such as Fe ²⁺ salt or sodium hydrogen sulfite is combined.

Although a water-soluble polymer is used as the dispersant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. Examples of the water-soluble polymer include synthetic polymers and natural water-soluble polymers, and any of them can be preferably used in the present invention. Among these, the synthetic water-soluble polymer includes, for example, those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, and nonionic groups. And those having a cationic group, those having an anionic group and a cationic group, and the like.
Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

As the natural water-soluble polymer, for example, those having a nonionic group, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group in the molecular structure, and nonionic Examples thereof include those having a cationic group and a cationic group, those having an anionic group and a cationic group, and the like.

As the water-soluble polymer, in both cases of synthetic water-soluble polymer and natural water-soluble polymer, those having an anionic group and those having a nonionic group and an anionic group can be preferably used.

In the present invention, the water-soluble polymer is 20 ° C.
It suffices to dissolve at least 0.05 g in 100 g of water,
It is preferably 0.1 g or more. Examples of the synthetic water-soluble polymer include those containing the repeating unit of the following general formulas (1) and / or (2) in an amount of 10 to 100 mol% in one molecule of the polymer.

[0092]

[Chemical formula 23]

In the formula, R ₁ represents a hydrogen atom, an alkyl group, a halogen atom or a —CH ₂ COOM group, preferably an alkyl group having 1 to 4 carbon atoms. L ₁ represents a divalent linking group, for example, -CONH-, -NHCO-, -C.
OO-, -OCO-, -CO-, -O-, etc. are mentioned. J ₁ represents an alkylene group, an arylene group, or an oxyalkylene group. Q ₁ is -OM, -NH _2, -SO
₃ M, -COOM, or

[0094]

[Chemical formula 24]

Represents --COOM and --SO ₃
M is preferably used in particular -SO ₃ M are preferable.
M represents a hydrogen atom or a cation (for example, an alkali metal ion, an ammonium ion), R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ have 1 to 20 carbon atoms.
Represents an alkyl group, and X ⁻ represents an anion. m ₁ and n
₁ represents 0 or 1, respectively. Y is a hydrogen atom or-
Represents (L ₂ ) m _2- (J ₂ ) n ₂ -Q ₂ , L ₂ , J ₂ , Q ₂ ,
m ₂ and n ₂ are synonymous with L ₁ , J ₁ , Q ₁ , m ₁ and n ₁ , respectively.

[0096]

[Chemical 25]

In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R
₂₆ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or —SO ₃ X, where X is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or ammonium. A group or an amino group, and R _{21 to} R ₂₆
At least one of —SO ₃ X.

The synthetic water-soluble polymer having the repeating units represented by the general formulas (1) and (2) may be a homopolymer of the units represented by the general formulas (1) and (2), It may contain other components.

Other components include, for example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, allyls. Examples thereof include compounds, vinyl ethers, vinyl ketones, glycidyl esters, unsaturated nitriles, and components in combination of two or more, preferably acrylic acid esters, methacrylic acid esters, and styrenes. Next, general formula (1)
Specific examples of the synthetic water-soluble polymer represented by (2) and (2) will be given.

[0100]

[Chemical formula 26]

[0101]

[Chemical 27]

[0102]

[Chemical 28]

Examples of natural water-soluble polymers that may be used in the present invention include those described in detail in the comprehensive technical data collection of water-soluble polymer water dispersion method resins (Management Development Center), but preferably lignin. , Starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum,
Gum arabic, laminaran, lichenin, nigran and the like and derivatives thereof. As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated and salts thereof are preferably used. Particularly preferred are glucose, gelatin, dextran, cellulose, pullulan, glucomannan, dextrin, gellan gum, locust bean gum, xanthan gum and derivatives thereof.

When polymerizing the composite latex of the present invention, it is preferable to use a metal alkoxide compound. Some metal alkoxide compounds are also called coupling agents, and various types such as silane coupling agents, titanium coupling agents, aluminum coupling agents, zirconium coupling agents are commercially available, but silane coupling agents are preferred. A ring agent and a titanium coupling agent.

Examples of preferable metal alkoxide compounds will be given below.

[0106]

[Chemical 29]

[0107]

[Chemical 30]

[0108]

[Chemical 31]

[0109]

[Chemical 32]

The composite latex of the present invention can be contained in the photographic constituent layer as it is or after being dissolved or dispersed in water. As a dispersion method, ultrasonic waves, a ball mill, an attritor, a pearl mill, a three-roll mill, a high speed grind device and the like can be preferably used.

The amount of the composite latex of the present invention used is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, based on the binder of the photographic component layer. The place of addition may be a light-sensitive layer or a non-light-sensitive layer as long as it is a silver halide emulsion layer.

Specific examples of the latex of the present invention are shown below, but the present invention is not limited to these.

[0113]

[Chemical 33]

[0114]

[Chemical 34]

[0115]

[Chemical 35]

Next, the slip agent used in the present invention will be described.

Typical slip agents used in the present invention include, for example, US Pat. No. 3,042,522 and British Patent 9
55,061, U.S. Pat. Nos. 3,080,317, 4,004,927, 4,047,958, 3,489,576, and British Patent 1,143,118.
No. 2, JP-A-60-140341 and the like, silicon-based lubricants, US Pat. Nos. 2,454,043 and 2,73.
2,305, 2,976,148, 3,20
6,311, German Patents 1,284,295, 1,
Higher fatty acid-based, alcohol-based, acid amide-based lubricants described in 284,294, etc., British Patent 1,263,722
No. 3, U.S. Pat. No. 3,933,516, and other metallic soaps, U.S. Pat. Nos. 2,588,765 and 3,121,0.
60, British Patent 1,198,387, etc., ester-based and ether-based lubricants, U.S. Pat. No. 3,502,43
There are taurine-based lubricants described in Nos. 7 and 3,042,222.

Specific examples of compounds of the slip agent used in the present invention are shown below, but the present invention is not limited thereto.

[0119]

[Chemical 36]

[0120]

[Chemical 37]

[0121]

[Chemical 38]

[0122]

[Chemical Formula 39]

These slip agents may be dispersed in the dispersant used and added in advance during the synthesis of the organic matting agent.

In the present invention, the method and amount of addition of the slip agent are not particularly limited, but they are preferably added in the hydrophilic colloid layer of the outermost surface layer of the silver halide photographic light-sensitive material.

The addition amount is one side of silver halide photographic light-sensitive material.
It may be 0.1 to 1000 mg per m ² , preferably 1
~ 500. Any addition method may be used, and it is preferable to add it in the coating liquid before coating.

A water-soluble polymer is contained in the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention.

The amount of the water-soluble polymer used is 50 mg to 800 mg, preferably 100 mg to 500 mg, per 1 m ^{2 on} one side of the silver halide photographic light-sensitive material. More preferably, it is 200 mg to 400 mg.

The water-soluble polymer referred to in the present invention means 20 ° C.
It suffices to dissolve at least 0.05 g in 100 g of
It is preferably 0.1 g or more.

Examples of the water-soluble polymer used in the hydrophilic colloid layer of the present invention include synthetic water-soluble polymers and natural water-soluble polymers, both of which are preferably used in the present invention. Among these, the synthetic water-soluble polymer includes, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure. Examples of the nonionic group include an ether group, ethylene oxide group, and hydroxy group, and examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Can be mentioned.

These synthetic water-soluble polymers may be not only homopolymers but also copolymers with one or more monomers. Furthermore, the composition of the copolymer with the partially hydrophobic monomer is slightly restricted by the place of addition and the amount thereof, as long as the copolymer itself retains water solubility. That is, particularly when a large amount is added to the emulsion layer, it is necessary to limit the composition range so that side effects do not occur during the addition.

The natural water-soluble polymers include, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.

It is preferable that the water-soluble polymer has a higher solubility in a developing solution or a fixing solution, and the solubility is 100 g of the developing solution.
On the other hand, 0.05 g or more is dissolved, preferably 0.5 g or more, and particularly preferably 1 g or more is dissolved.

As the synthetic water-soluble polymer, a repeating unit represented by the following general formula (P) is used in an amount of 10 to 100 in one molecule of the polymer.
The thing containing mol% is mentioned.

[0134]

[Chemical 40]

In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent. For example, a methyl group , Ethyl group, propyl group, butyl group, etc.), halogen atom (eg chlorine atom) or --CH ₂
Represents COOM, L is -CONH-, -NHCO-,-
COO -, - OCO -, - CO -, - SO 2 -, - NH
SO ₂ −, —SO ₂ NH— or —O— is represented, and J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a substituent. For example, methylene group, ethylene group, propylene). Group, trimethylene group, butylene group, hexylene group, etc.), arylene group (including those having a substituent, for example, phenylene group, etc.), aralkylene group.

[0136]

[Chemical 41]

M represents a hydrogen atom or a cation group, and R
₉ is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
An ethyl group, a propyl group, a butyl group, etc.), R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc. ), An alkenyl group (eg, vinyl group, allyl group, etc.), a phenyl group (eg, phenyl group, methoxyphenyl group, chlorophenyl group, etc.), an aralkyl group (eg, benzyl group), X ⁻ represents an anion, and p − And q each represent 0 or 1. Polymers containing acrylamide or methacrylamide are particularly preferred.

Y is a hydrogen atom or-(L) _p- (J) _q -Q
Represents

In addition, the synthetic water-soluble monomer of the present invention can be copolymerized with an ethylenically unsaturated monomer. Examples of the copolymerizable ethylenically unsaturated monomer include styrene, alkylstyrene, hydroxyalkylstyrene (alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, butyl, etc.), vinylbenzenesulfonic acid and salts thereof, α-Methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of fatty acids (eg vinyl acetate, vinyl propionate, etc.) Ethylenically unsaturated monocarboxylic acids or dicarboxylic acids and salts thereof (eg acrylic Acid, methacrylic acid) maleic anhydride, ester of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (for example, n-butyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate), ethylenically unsaturated of Nokarubon acid or amides of dicarboxylic acids (e.g., acrylamide, 2-acrylamido-2-methylpropane sulfonic acid sodium,
N, N-dimethyl-N'-methacryloylpropanediamineacetate betaine) and the like.

Next, specific examples of the synthetic water-soluble polymer represented by the general formula (P) will be given.

[0141]

[Chemical 42]

[0142]

[Chemical 43]

[0143]

[Chemical 44]

[0144]

[Chemical formula 45]

[0145]

[Chemical formula 46]

The number average molecular weight of the synthetic water-soluble polymer of the present invention is not particularly limited and is preferably 30,000.
It is 0 or less, preferably 15,000 or less.

As the natural water-soluble polymer, it is described in detail in a collection of technical data on water-soluble polymer water-dispersible resin (published by the Management Development Center). Lignin, starch, pullulan, cellulose, alginic acid, dextran, Dextrin, guar gum, gum arabic, pectin, casein, agar, xanthan gum, cyclodextrin, locust bean gum, tragacanth gum, carrageenan,
Glycogen, laminaran, lichenin, nigeran and the like, and derivatives thereof are preferred.

As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, or carboxyalkylenated, alkylphosphorylated, and salts thereof, polyoxyalkylenated (eg, ethylene, glycerin). , Propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.) are preferred.

In the present invention, the natural water-soluble polymer is 2
You may use it in combination of 2 or more types.

Among the natural water-soluble polymers, glucose polymer and its derivative are preferable, and among glucose polymer and its derivative, starch, glycogen,
Cellulose, lichenin, dextran, dextrin,
Cyclodextrin, nigeran and the like are preferable, and dextrin, cyclodextrin and derivatives thereof are particularly preferable.

The amount of the synthetic or natural water-soluble polymer used in the present invention is 0.01 to 2 per side.
g / m ² is preferable, but more preferably 0.05 to 1 g
/ M ² . More preferably, it is 0.1 to 0.5 g / m ^2.
Is. The layer to be added is preferably an emulsion layer, but may be added in a necessary amount to other hydrophilic colloid layers if necessary.

The synthetic or natural water-soluble polymer used in the present invention may be used alone, or may be used in combination of two or more kinds if necessary.

The synthetic or natural water-soluble polymer used in the present invention is contained in the photographic light-sensitive material in an amount of 10% or more, preferably 10% or more and 30% or less of the total weight of the photographic light-sensitive material.

The dextrin used in the present invention is α-
It is a polymer of 1,4-bonded D-glucose, and generally refers to a general term for various decomposition products from hydrolysis of starch to maltose. It has no particular structural characteristics, and its molecular weight is not constant, except that some are structurally important as academically important. There are many types, depending on the method and application of hydrolysis, from high molecular weight ones obtained by slightly hydrolyzing starch to low molecular weight ones which do not exhibit iodine starch reaction.

Specific examples of dextrins are trade names such as LLD from Meito Sangyo Co., Ltd., trade names such as Amycor 1 and Dextrin 102S from Nitto Kagaku Co., Ltd.
In addition, those commercially available from Towa Kasei Kogyo Co., Ltd. under the trade name of PEO and the like can be mentioned.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention contains a latex.

As the latex used in the present invention,
As the ethylenic monomer compound forming the polymer latex, for example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters,
Maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, various unsaturated acids The monomer compound which combined 1 type or 2 types or more can be mentioned.

More specifically, these monomer compounds are exemplified by acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, 2-chloro Cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2- Mud carboxyethyl acrylate, 5
Hydroxypentyl acrylate, 2,2-dimethyl-
3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate,
2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate,
2- (2-methoxyethoxy) ethyl acrylate, 2
-(2-butoxyethoxy) ethyl acrylate, ω-
Methoxy polyethylene glycol acrylate (additional mol number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate and the like can be mentioned.

Examples of methacrylic acid esters are methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl. Methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate. , 2-ethoxyethyl methacrylate, 2-iso Propoxyethyl methacrylate,
2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (addition mole number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate salt of methacrylic acid and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1
-Pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and the like can be mentioned.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene. , Vinyl benzoic acid methyl ester and the like.

Examples of crotonic acid esters include butyl crotonic acid, hexyl crotonic acid and the like.

Examples of diethyl itaconates include dimethyl itaconate, diethyl itaconate and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diesters include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethyl. Acrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like; methacrylamides such as methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide,
Cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl ) Methacrylamide and the like; allyl compounds, such as allyl acetate, allyl caproate, allyl laurate and allyl benzoate; vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether; vinyl ketone Classes such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl Ketones and the like; vinyl heterocyclic compounds such as vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone and the like; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; unsaturated nitriles Classes such as acrylonitrile, methacrylonitrile and the like; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide,
Ethylene glycol dimethacrylate etc.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrene sulfonic acid, vinyl benzyl sulfonic acid, vinyl sulfonic acid, acryloyloxy Alkyl sulfonic acids such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid and the like; methacryloyloxyalkyl sulfonic acids such as methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid and the like; Acrylamide alkyl sulfonic acid, such as 2-acrylamido-2-methylethane sulfonic acid, 2- Acrylamide-2-methylpropanesulfonic acid, 2-acrylamido-2-methyl butanoic acid; methacrylamide alkyl sulfonic acid,
For example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, and the like; acryloyloxyalkyl phosphate, such as acryloyloxyethyl phosphate, 3
-Acryloyloxypropyl-2-phosphate, etc .; methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc .; 3-allyloxy-2-hydroxypropanesulfonic acid naphthyl, etc. having two hydrophilic groups Is mentioned. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Pat. Nos. 3,459,790, 3,438,708, 3,554,987, 4,215,195 and 4,247,673. The crosslinkable monomers described in JP-A-57-205735 and the like can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide.

Of these monomer compounds, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins are preferably used.

Specific examples of the latex preferably used in the present invention are shown below, but the latex is not limited thereto.

[0168]

[Chemical 47]

[0169]

[Chemical 48]

[0170]

[Chemical 49]

[0171]

[Chemical 50]

[0172]

[Chemical 51]

[0173]

[Chemical 52]

[0174]

[Chemical 53]

The average particle size of the polymer latex used in the present invention is particularly preferably 0.01 to 0.8 μm, and 0.0
Any material having a thickness of 05 to 2.0 μm can be used.

The particle size of the polymer latex used in the present invention is the electron microscopic method described in "Chemistry of Polymer Latex" (Kobunshi Kogakukai, 1973),
It can be measured by a soap titration method, a light scattering method, or a centrifugal sedimentation method, and the light scattering method is preferably used. As a device for the light scattering method, DLS700 (manufactured by Otsuka Electronics Co., Ltd.) was used.

The molecular weight is not particularly specified, but the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000.

The polymer latex used in the present invention can be contained in the photographic constituent layer as it is or after being dispersed in water.

The amount of hydrazine derivative used in the light-sensitive silver halide emulsion layer and / or the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is represented by the following general formula [H]. Compounds.

[0180]

[Chemical 54]

In the general formula [H], A ₀ is an aliphatic group,
The aromatic group or heterocyclic group, and the aliphatic group represented by A ₀ preferably have 1 to 30 carbon atoms, and particularly 1 to 2 carbon atoms.
A straight chain, branched chain or cyclic alkyl group of 0 is preferable, and specific examples thereof include a methyl group, an ethyl group, a t-butyl group,
Examples thereof include an octyl group, a cyclohexyl group, a benzyl group and the like, which are further substituted with a suitable substituent (eg, aryl, alkoxy, aryloxy, alkylthio, arylthio, sulfoxy, sulfonamide, sulfamoyl, acylamino, ureido group, etc.). May be.

[0182] In formula (H), the aromatic group represented by A ₀ is an aryl group preferably a monocyclic or condensed, such as a benzene ring or a naphthalene ring can be mentioned, A ₀
The heterocyclic group represented by is a monocyclic or condensed ring nitrogen atom,
Sulfur, preferably a heterocycle containing at least one heteroatom selected from oxygen atoms, for example pyrrolidine, imidazole, tetrahydrofuran, morpholine, pyridine,
Pyrimidine, quinoline, thiazole, benzothiazole, thiophene, furan ring and the like can be mentioned. Particularly preferred as A ₀ are aryl group and heterocyclic group,
The aromatic group and heterocyclic group of ₀ may have a substituent, and a particularly preferable group is a substituent having an acidic group of pKa7 or more and 11 or less, specifically, a sulfonamide group,
Examples thereof include a hydroxyl group and a mercapto group.

Further, in the general formula [H], A ₀ preferably contains at least one diffusion resistant group or silver halide adsorbing group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is a photographically inactive group having 8 or more carbon atoms, such as an alkyl group, an alkenyl group or an alkynyl group, Examples thereof include an alkoxy group, a phenyl group, a phenoxy group and an alkylphenoxy group.

In the general formula [H], the silver halide adsorption promoting group is a thiourea, a thiourethane group, a mercapto group, a thioether group, a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, or a special group. Kaisho 64-9
Examples thereof include the adsorption group described in No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably -G ₀ -D ₀ group, and G ₀ represents-.
CO- group, -COCO- group, -CS- group, -C (= NG
₁ D ₁ ) -group, —SO— group, —SO ₂ — group or —P (O)
Preferred G ₀ , which represents a (G ₁ D ₁ ) -group, is —CO—.
Group, particularly preferably at -COCO- group -COCO- group and the like, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - represents a group, D ₁ is an aliphatic Group, aromatic group,
When a plurality of D _1's are present in the molecule and represent a heterocyclic group or a hydrogen atom, they may be the same or different.

In the general formula [H], D ₀ is a hydrogen atom,
It represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group, and preferable D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like, and A ₁ , A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl,
(Trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl, etc.).

A more preferred embodiment of the compound represented by the general formula [H] is the compound represented by the general formula [H-2].

General formula [H-2] R ₀ -SO ₂ NH-Ar-NHNH-G ₀ -D _{0 In the} general formula [H-2], R ₀ is a substituted or unsubstituted alkyl group, aryl group, or hetero group. Represents a cyclic group, Ar represents a substituted or unsubstituted divalent arylene group, a heterocyclic group,
G ₀ and D ₀ have the same _{meaning as} in general formula [H].

Specific examples of the compound represented by the general formula [H] are shown below, but the invention is not limited thereto.

[0190]

[Chemical 55]

[0191]

[Chemical 56]

[0192]

[Chemical 57]

[0193]

[Chemical 58]

[0194]

[Chemical 59]

In the present invention, it is essential to use a nucleation accelerator in order to effectively promote the contrast enhancement by hydrazine. A preferred nucleation accelerator is represented by the following general formula
The compound represented by a] or [Nb] is preferably used.

[0196]

[Chemical 60]

In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
It represents a substituted aryl group, and R ₁₁ , R ₁₂ , and R ₁₃ can form a ring.

Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is particularly preferable. Further, preferable adsorption groups include a heterocycle, a mercapto group, a thioether group, a selenoether group, a thione group and a thiourea group.

Specific examples of the compounds of these nucleation accelerators [Na] are shown below.

[0200]

[Chemical formula 61]

[0201]

[Chemical formula 62]

[0202]

[Chemical formula 63]

As a preferable embodiment of [Na], a compound represented by the following general formula [Na2] can be mentioned.

[0204]

[Chemical 64]

In the general formula [Na2], R ₁ , R ₂ and R
₃ or R ₄ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, a substituted aryl group, a saturated or unsaturated heterocycle, and these are linked to each other. To form a ring, and R ₁ , R ₂ or each pair of R ₃ and R ₄ are not hydrogen atoms at the same time.

In the general formula [Na2], X is S or Se.
Alternatively, it represents a Te atom, and L ₁ and L ₂ represent a divalent linking group.
Specific examples include groups having the following combinations of groups and substituents of the groups (for example, alkylene group, alkenylene group, arylene group, acylamino group, sulfonamide group, etc.).

[0207] _{-CH 2 -, - CH = CH} -, - C 2 H
₄ -, _{pyridiyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, - S -, -
(CO) -, - (SO 2) -, - CH 2 N-, also preferably contains at least one or more of the following structure in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ ).
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
[OCH ₂ C (OH) HCH ₂ ] -In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group, and R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group. Although Ar and R ₁₄ may be linked by a linking group to form a ring, these compounds preferably have a diffusion resistant group or a silver halide adsorbing group in the molecule, and have preferable diffusion resistance. The molecular weight for imparting is preferably 120 or more, and particularly preferably 300 or more. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

Specific examples of the compound of the general formula [Nb] include those shown below.

[0210]

[Chemical 65]

[0211]

[Chemical formula 66]

In the present invention, when a nucleation accelerator having a molecular weight of 500 or less is used, the effect of the present invention is more exerted.

The addition layer of the hydrazine derivative and the nucleation accelerator of the present invention is a silver halide emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer.

The optimum amount of addition is not uniform depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but generally it is 10 per mol of silver halide. The range of ^-6 mol to 10 ^-1 mol is preferable, and the range of 10 ^-5 mol to 10 ^-2 mol is particularly preferable.

Other preferable nucleation accelerators include onium salt compounds described in JP-A-7-270957, compounds of general formula I described in JP-A-7-104420,
JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and thiosulfonic acid compounds described in JP-A-1-237538. To be

The redox DIR compound capable of releasing a development inhibitor by being oxidized according to the present invention will be described.

The redox DIR compound of the present invention has a partial structure such as hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and α-aminoketones as a redox group.

As preferable redox DIR compound,
NH NH-group-containing compound and the following general formula [3],
It is a compound represented by [4], [5], [6], [7] or [8].

[0219]

[Chemical formula 67]

The DIR compound having a -NHNH- group as a redox group is represented by the following general formula [RE-a] or [RE-b].

General formula [RE-a] T-NHNHCO- (Tm) _n -PUG General formula [RE-b] T-NHNHCOCO- (Tm) _n -PUG General formula [RE-a], [RE-b] In the above, T represents an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. As a preferable substituent, a linear or branched alkyl group (preferably having a carbon number of 2 to 20) is used. Such as methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy group (preferably having 2 to 21 carbon atoms, for example, methoxy group, ethoxy group etc.), aliphatic acylamino group (preferably having 2 to 21 carbon atoms) Those having a group, such as acetylamino group, heptylamino group, etc.), aromatic acylamino groups, and the like. In addition to these, the substituted or unsubstituted aromatic ring as described above is -CONH-, -O-. ,-
It also includes those linked by a linking group such as SO ₂ NH-, -NHCONH-, and -CH ₂ CHN-. Tm represents a timing group, and n represents 0 or 1. PUG becomes a compound exhibiting a development inhibitory property when released, and as a development inhibitory compound, 5-nitroindazole,
4-nitroindazole, 1-phenyltetrazole,
1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole,
Examples include 5-nitroimidazole and 4-nitroimidazole. These development-inhibiting compounds are T-NHN
To the -CO- or -COCO- moiety to which the H- group is bonded, directly bonded via a hetero atom such as N or S, or bonded via an alkylene, phenylene, aralkylene, or arylene group, and further via a hetero atom such as N or S. As a result, it is possible to control the timing until the development inhibitory property is exhibited after the separation. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecylethylene oxide thiopropionic acid amide) -5- (5-
Nitroindazol-2-yl) hydroquinone, 2-
(Stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t
-Amylphenoxypropionic acid amide) -5- (5-
Nitrotriazol-2-yl) hydroquinone, 2-
Dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone and the like can be mentioned.

The above redox DIR compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

The redox DIR compound can be used in any layer as long as it is a photographic constituent layer on the silver halide emulsion layer side. It is preferably used in the silver halide emulsion layer closest to the support and / or in the non-photosensitive hydrophilic colloid layer adjacent to the support side of the emulsion layer.

The addition of the redox DIR compound described above
Dissolve in alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, esters such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. Can be added later. Further, those which are difficult to dissolve in water or an organic solvent can be arbitrarily dispersed with an average particle diameter of 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For the dispersion, a surface active agent such as anion or nonion, a thickener, a latex and the like can be added and dispersed.

The addition amount of the above redox DIR compound is
It is from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 to 10 ^-2 mol, per mol of silver halide.

Among the compounds represented by formula [RE-a] or [RE-b], particularly preferable compounds are shown below.

[0227]

[Chemical 68]

[0228]

[Chemical 69]

Specific examples of other preferable redox DIR compounds include 2 of JP-A-4-245243.
36 (8) page "0053" to 250 (22) page "006"
R-1 to R-50 described in "8".

Next, the general formulas [3], [4],
The redox DIR compound represented by [5], [6], [7] or [8] will be described.

General formulas [3], [4], [5], [6],
In [7] or [8], R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₂ and R ₁₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₁₄ represents a hydrogen atom. R ₁₅ to R ₁₉ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃ represent a substituent capable of substituting on the benzene ring. X ₄ , X
₅ represents O or NH. Z represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W represents N (R ₅₀ ) R ₅₁ or OH, and R ₅₀ and R ₅₁ are a hydrogen atom, an alkyl group,
It represents an aryl group or a heterocyclic group. COUP is the first aromatic
It represents a coupler residue capable of causing a coupling reaction with an oxidized product of a primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group. m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4.
n represents 0 or 1. PUG represents a group which is released and becomes a development inhibiting compound.

The above general formulas [3], [4], [5],
In [6], [7] or [8] (hereinafter, in the formula), R
_The alkyl group, aryl group and heterocyclic group represented by ₁₁ , R _{15 to} R ₁₉ , R ₅₀ and R ₅₁ are preferably methyl group, p-
Examples thereof include a methoxyphenyl group and a pyridyl group. R ₁₂
And an acyl group represented by R ₁₃ , a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group, preferably an acyl group, a carbamoyl group, It is a cyano group. The total carbon number of these groups is preferably 1-20. R _{11 to} R ₁₉ , R ₅₀ ,
R ₅₁ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group,
Hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group ( For example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.),
Cyano group, acylamino group (for example, acetylamino group,
Propionylamino group etc.), alkylthio group (eg methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group) Group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg fluorine group). Nonoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group) , Dimethylamino group, etc.), hydroxyl group, nitro group, imide group (eg phthalimide group etc.), heterocyclic group (eg pyridyl group,
Benzimidazolyl group, benzthiazolyl group, benzoxazolyl group and the like). Examples of the coupler residue represented by COUP include the following.
Examples of cyan coupler residues include phenol couplers and naphthol couplers. 5 for magenta coupler
-Pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, indazolone couplers and the like. As a yellow coupler residue, a benzoylacetanilide coupler,
There are pivaloyl acetanilide couplers, malondianilide couplers and the like. Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.). Further COUP
Among the coupler residues represented by, those which are preferably used in the present invention can be represented by the general formula (Coup-1) to the general formula (Coup-8).

[0233]

[Chemical 70]

In the formula, R ₅₆ represents an acylamido group, anilino group or ureido group, and R ₅₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0235]

[Chemical 71]

In the formula, R ₅₈ and R ₅₉ represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfouride group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₆₀ and R ₆₁ are each a fatty acid group. It represents a group group, an aromatic group or a heterocyclic group. Further, one of R ₆₀ and R ₆₁ may be a hydrogen atom. a is an integer of 1 to 4, b
Represents an integer of 0 to 5. When a and b are plural, R ₅₈ may be the same or different, and R ₅₉ may be the same or different.

[0237]

[Chemical 72]

In the formula, R ₆₂ represents a tertiary alkyl group or an aromatic group, and R ₆₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₆₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0239]

[Chemical formula 73]

In the formula, R ₆₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₆₆ represents a hydrogen atom, a halogen atom or a nitro group.

[0241]

[Chemical 74]

R ₆₇ and R ₆₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

5 to 6 represented by Z in the general formula [4]
The membered heterocyclic ring may be a monocyclic ring or a condensed ring, and may be O,
5 to 6 having at least one kind of S and N atoms in the ring
Member heterocycle. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm in the general formulas [3] to [8] is preferably —OCH ₂ — or another divalent timing group, for example, US Pat.
No. 8,962, No. 4,409,323, or No. 3,6
74,478, (RD) No. 21228 (1981
December 2012), or JP-A-57-56837 and JP-A-4.
-438, etc. are mentioned.

Preferred development inhibitors for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336.
No. 50, or the development inhibitor described in No. 61-11743.

Specific examples of the compounds represented by the general formulas [3] to [8] are listed below, but the present invention is not limited thereto.

[0247]

[Chemical 75]

[0248]

[Chemical 76]

[0249]

[Chemical 77]

[0250]

[Chemical 78]

[0251]

[Chemical 79]

[0252]

[Chemical 80]

The compounds represented by the above formulas [3] to [8] can be used in any of the layers as long as they are photographic constituent layers on the silver halide emulsion layer side. It is preferably used in the silver halide emulsion layer closest to the support and / or in the non-photosensitive hydrophilic colloid layer adjacent to the support side of the emulsion layer.

The compounds represented by the above general formulas [3] to [8] are suitable water-miscible organic solvents such as alcohols,
It can be used by dissolving it in ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. It is also possible to add it as an emulsified dispersion using a known oil. Further, the compound powder may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves by a method known as a solid dispersion method.

The addition amount of the compounds represented by the above general formulas [3] to [8] is from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 to 1 ^-1 mol per mol of silver halide.
It is in the range of 0 ^-2 mol.

The silver halide composition of the silver halide photographic light-sensitive material of the present invention is pure silver chloride, silver chlorobromide having a silver chloride content of 60 mol% or more, or salt having a silver chloride content of 60 mol% or more. It is preferably silver iodobromide.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.1 to 0.5 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. What is particle size?
When the particles are spherical or can be approximated to a sphere, the particle diameter is meant. If the particle is a cube, convert it to a sphere,
Let the diameter of the sphere be the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE Mee).
s & T. H. James: The theory o
f the photographic processes
s), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. A silver halide emulsion having a uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing an element of Groups 3 to 13 of the periodic table, such as osmium salt, iron salt, copper salt, platinum salt and palladium salt. As the ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used.

The surface of the silver halide grains can be controlled in halogen composition by using a water-soluble halide or fine silver halide grains. This method is called conversion in the art and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen composition, dopant species and amount, distribution of lattice defects and the like.

In the present invention, as the silver halide grains, grain size, sensitivity, crystal habit, photosensitive wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, desalting method and the like are manufactured. A plurality of types of particles having different conditions, surface states, chemically sensitized states and the like can be used in combination. In that case, these silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (RD).
17643, pages 22 to 23 (December 1978) or cited therein.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazoline thione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3) , 3a, 7-Tetrazaindenes), pentazaindenes and the like; many known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like. Compounds can be added. Particularly preferred is a substituted or unsubstituted heterocycle or heterocondensed ring containing any of N, O, S, and Se, and a water-soluble halide.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin. , Issia Over preparative acids, the carboxyl group activated hardeners, etc., may be used alone or in combination.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Various other additives are used in the light-sensitive material used in the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and colloidal silica.

Regarding these additives and the above-mentioned additives, specifically, those described on pages 22 to 31 of RD17643 can be used.

When the silver halide photographic light-sensitive material of the present invention is applied to a silver halide photographic light-sensitive material for plate-making printing, the compounds described below are used in the constituent layers of the silver halide photographic light-sensitive material. You can

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3), pages [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group JP-A-62-237445, compound described on page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
To the compound (4) sensitizing dye described in [0062] on page (17) (however, of the following, the spectral sensitization maximum is 60).
Dye of 0 to 900 nm) JP-A-5-224330, page (3) [0017]-
Compound described on page (13), page [0040], JP-A-6-194771, page (11), page [0042]
-Compounds described on page (22), page [0094], JP-A-6-242533, page (2), page [0015]-
(8) compound described on page [0034], JP-A-6-337492, page (3), page [0012] to
Compound described on page (34), page [0056], JP-A-6-337494, page (4), page [0013] to
Compound (5) Supersensitizer described on page (14), page [0039] JP-A-6-347938, page (3), page [0011] to
Compound (6) Tetrazolium compound described on page (16), page [0066] JP-A-6-208188, page (8), page [0059] to
Compound (7) Pyridinium compound described on page (10), page [0067] JP-A-7-110556, page (5), page [0028] to
Compound (8) Redox compound described on page (29), page [0068] JP-A-4-245243, 235 (7) to 250
(22) The compound described on page.

In the light-sensitive material of the present invention, the photographic constituent layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored contents), or polyethylene or polyethylene. For example, a paper support coated with a polymer such as terephthalate. These supports may have a magnetic recording layer, an antistatic layer and a release layer.

As developing agents that can be used in the method for processing a light-sensitive material of the present invention, dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone,
Bromhydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-).
p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-
3-Pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyra) Zoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.),
Transition metal complex salts (Ti, V, Cr, Mn, Fe, Co,
It is a complex salt of a transition metal such as Ni or Cu, and these may be in a form having a reducing power for use as a developing solution. For example, a complex salt of Ti ³⁺ , V ²⁺ , Cr ²⁺ , Fe ²⁺ or the like may be used. It takes a form, and as a ligand, ethylenediaminetetraacetic acid [EDT
A], aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid [DTPA] and salts thereof, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof, and the like. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, It is preferable to use a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844,
No. 4-26838, No. 4-362942, No. 1-3
The compounds described in No. 19031, No. 7-13303 and the like can be mentioned.

Further, the waste developer can be regenerated by energizing it. Specifically, put a negative electrode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste solution and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution, and perform anion exchange. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developer, are additionally added. You can do it. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the developer waste liquid is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the developing solution include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. Dissolution aids (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,
No. 025, Japanese Patent Publication No. 47-45541, etc.), a hardener (eg glutaraldehyde or its bisulfite adduct), or an antifoaming agent can be added.

As the fixing solution, those having a generally used composition can be used. As the fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate can be used. In addition to thiocyanates such as the above, it is possible to use an organic sulfur compound capable of forming a soluble stable silver complex salt, which is known as a fixing agent. Water-soluble aluminum salt that acts as a hardener in the fixer,
For example, it may contain aluminum chloride, aluminum sulfate, potassium alum, etc., and if desired, a preservative (eg sulfite, bisulfite), pH buffer (eg acetic acid), pH adjuster (eg sulfuric acid). A compound such as a chelating agent having the ability to soften water can be included.

In the developing treatment, washing is carried out after fixing, but the washing layer may be a system in which fresh water is supplied at a rate of several liters per minute depending on the treatment, or washing water is circulated, chemicals, a filter or ozone is used. A method of reusing by treating with light or the like, or a method of replenishing a washing bath with a small amount of a stabilizing solution as a stabilizing bath containing a stabilizer is used.

As the mother liquor or replenisher for the developer, fixer, stabilizer, it is usual to supply the working solution or the concentrate diluted immediately before. The stock of mother liquor or replenisher may be in the form of a working liquid or a concentrated liquid, a viscous liquid with a high viscosity in a semi-kneaded state, or a system in which a simple substance or a mixture of solid components is dissolved at the time of use. When the mixture is used, it is possible to use a method in which components that are difficult to react with each other are packed adjacent to each other in a layered form and then vacuum-packaged to be opened and dissolved at the time of use, or a tableting method. In particular, the method of adding the tablet-formed product to the dissolution layer or directly to the treatment layer is
The method is extremely excellent in terms of space saving and preservability, and can be used particularly preferably.

In the processing method of the present invention, the developing temperature is set to 2
It can also be set in a normal temperature range of 0 to 50 ° C.
The silver halide photographic light-sensitive material of the present invention is preferably processed using an automatic processor. At that time, processing is performed while replenishing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The developing replenishing amount and the fixing replenishing amount are 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. It is preferably 75 to 200 ml per 1 m ² .

In the present invention, in order to shorten the developing time, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 10 when the processing is performed using the automatic developing machine. It is preferably -60 seconds.

I'm sorry.

In the processing method of the present invention, the pH of the developing solution is adjusted to 9.5 to 11.0. More preferably 9.6
~ 10.9. By processing in this pH range, a high contrast image having a gamma of 10 to 30 is formed.

[0286]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A1) The average diameter of silver chloride 70 mol% and the balance silver bromide 0.0
9 μm silver chlorobromide core particles were prepared. _{K 3 Rh (NO) 4 (} H 2 O) 7 × 10 -8 mol ₂ per mol of silver when silver mole per grain formation ended when the core particle mixture, K ₃ Os
Cl ₆ at 40 ° C., pH in the presence of 8 × 10 ⁻⁶ mol addition
While maintaining the silver potential (EAg) at 165 mV at 3.0, the silver nitrate aqueous solution and the water-soluble halide solution were simultaneously mixed.

EAg was added to the core particles in an amount of 125 m with sodium chloride.
Lowered to V and shelled using the double-mix method. At that time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ⁻⁷ per mol of silver.
9 × 10 ⁻⁸ mol of K ₃ RhCl ₆ was added. Further, KI conversion was carried out using fine silver iodide grains, and the resulting emulsion had a core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide (silver chloride 70 mol%, average diameter 0.15 μm,
The emulsion was a cubic crystal composed of 0.2 mol% of silver iodobromide and the rest consisting of silver bromide. Then, modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-28013)
No. 9, 287 (3), Exemplified Compound G-8) was used for desalting. The EAg after desalting was 190 mV at 50 ° C.

In the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide in an amount of 8.5 × 10 5.
^-4 mol and citric acid added, pH 5.6, EAg12
After adjusting to 3 mV, 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added and reacted, and then inorganic sulfur S8 dispersed in solid was added.
1. An appropriate amount of a compound (a mixture of water and a sulfur-methanol solution dispersed in water having an average particle size of 0.3 μm) and chloroauric acid were added to 1.
After 5 × 10 ^-5 mol was added and chemical ripening was carried out at a temperature of 55 ° C. until the maximum sensitivity was obtained, the sensitizing dye d-1 was added at 50 ° C.
00mg, trihexylamine 5mg added, 40 more
After the temperature was lowered to ℃, 4-hydroxy-6-methyl-1,
2,3a, 7-tetrazaindene is added 2 × per mol of silver
10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3 × 10 ^-4 mol and potassium iodide addition 5 × 10 ^-3
After adding mols, the pH was adjusted to 5.1 with citric acid.

(Preparation of Silver Halide Emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μm, and K ₃ RhCl ₆ in the shell portion was adjusted to 6 × 10.
^-Silver Halide Emulsion A in exactly the same manner except that the amount was ^-8 mol.
2 was prepared. The emulsion of A2 is 40% more sensitive than the emulsion of A1 when subjected to the same chemical sensitization.

(Preparation of silver halide photographic light-sensitive material containing hydrazine derivative for printing plate making scanner) A backing layer having the following formulation 5 and a gelatin amount of 1 was formed on the undercoat layer of the support on the side opposite to the emulsion layer. To be 0.5 g / m ² ,
A backing protective layer having the following Formulation 6 was coated on the emulsion layer side simultaneously with the emulsion coating side at a speed of 200 m / min by a curtain coating method so that the amount of gelatin would be 0.8 g / m ² , and then cooled and set. After that, the backing layer side was simultaneously coated in multiple layers, cooled and set at -1 ° C, and both surfaces were dried at the same time to obtain a sample.

[0292] Formulation 1 (gelatin subbing layer composition) Gelatin 0.45 g / m ² Saponin 56.5 mg / m ² sodium polystyrenesulfonate (average molecular weight 500000) 15 mg / m ² fungicide z 0.5 mg / m ² Formulation 2 (Composition of silver halide emulsion layer 1) Gelatin 0.65 g / m ² Silver halide emulsion A1 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-1 200 mg / Ag 1 mol Hydrazine compound H-1 2 × 10 ^-3 mol / Ag 1 mol Amino compound AM-1 7 mg / m ² redox compound No. 21 70 mg / m ² compound a 100 mg /
m ² 2-pyridinol 1 mg / m ² polymer latex L1 (particle size 0.25 μm) 0.25 g / m ² hardener h1 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² Sodium naphthalene sulfonate 8 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyrimidine 1 mg / m ² colloidal silica (average particle size 0.05 μm) 150 mg / M ² Ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² Coating solution pH was 5.2.

The redox compound was used after being dispersed by the following dispersing method.

(Method for Dispersing Redox Compound) Redox compound 2 g Ethyl acetate 80 g The redox compound was dissolved in the above formulation and mixed with the following gelatin solution.

10% TK-AX (manufactured by Takemoto Yushi Co., Ltd.) 6 g 15% aqueous gelatin 180 g After preliminarily dispersing the mixed solution at 40 ° C. for 5 minutes with a homogenizer, the main dispersion was performed and the pressure was reduced to 130 mmHg to remove ethyl acetate. Remove. Make up to 280 g with water.

Formulation 3 (Composition of silver halide emulsion layer 2) Gelatin 0.65 g / m ² Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-2 300 mg / Ag 1 mol Hydrazine compound H -2 4 x 10 ^-3 mol / Ag 1 mol Amino compound AM-1 7 mg / m ² redox compound No. 21 70 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² nicotinic acid amide 1 mg / m ² gallic acid n-propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² latex L2 <Compound described in Example 3 of JP-A-5-66512, type Lx-3 Composition (9)> 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² composite latex (Ex. PL-10) 0.2 g / m ² Gelatin is phthalated gelatin, and coating solution pH Is 4.
It was 8.

Formulation 4 (Emulsion protective layer composition) Gelatin 1.3 g / m ² Amino compound AM-1 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle size 3 0.5 μm spherical polymethylmethacrylate 25 mg / m ² average particle size 8 μm indeterminate silica 12.5 mg / m ² surfactant S1 26.5 mg / m ² lubricant (silicone oil) 4 mg / m ² compound a 50 mg / m ² Polymer latex L4 (particle diameter 0.10 μm) 0.25 g / m ² colloidal silica (average particle diameter 0.05 μm) 150 mg / m ² dye f1 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardener h2 30 mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide z 0.5 mg / m ² composite latex Illustrative PL-10) 0.2g / m ² formulation 5 (Backing layer composition) Gelatin 0.6 g / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 100 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² 1-Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h 3 100 mg / m ² composite latex (Ex. PL-10) 0.4 g / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Formulation 6 (backing protective layer) Gelatin 0.4 g / m ² matting agents, average particle size: 5μm monodispersed polymethyl methacrylate 50 mg / ^{m 2} the average particle diameter of 3μm indeterminate system Siri 12.5 mg / m ² Sodium - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² Surfactant S1 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² Compound a 50 mg / m ² Hardener h2 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ^{2 When a} solid disperse dye is added, the dye exemplified SF2 is citric acid which is 1.2 times equivalent to the acid group after being dissolved in alkali. Was added for acid precipitation. Other dyes (including those after Example 2) were dispersed with ZrO beads to obtain a powder dispersion having a particle size of 0.1 μm.

In the above basic coating formulation, sample No. having the following coating pattern was used. A to D were prepared. The amount of silver coated on each sample was 3 g / m ² . The amount of gelatin applied was 3.05 g / m ² .

Sample No. A: Simultaneous coating of two silver halide emulsion layers of Formula 3 and a protective layer of Formula 4 thereon B: Gelatin subbing layer of Formula 1, silver halide emulsion layer of Formula 3 thereon, and further thereon Simultaneous coating of three protective layers of Formula 4 C: Gelatin subbing layer of Formula 1, silver halide emulsion layer of Formula 2 thereon, silver halide emulsion layer of Formula 3 thereon, and formula thereon Simultaneous coating of 4 protective layers in total D: Gelatin subbing layer of formulation 1, silver halide emulsion layer of formulation 2 thereon, gelatin layer same as formulation 1 thereon, and halogen of formulation 3 thereon. Simultaneous coating of a total of 5 silver halide emulsion layers and a protective layer of Formula 4 thereon.

[0300]

[Chemical 81]

[0301]

[Chemical formula 82]

[0302]

[Chemical 83]

[0303] (Developer composition) Per 1 liter of solution used   Diethylene-triamine pentaacetic acid-5 sodium salt 1g   Sodium sulfite 42.5g   Potassium sulfite 17.5g   55 g of potassium carbonate   Hydroquinone 20g   1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone                                                           0.85g   Potassium bromide 4g   5-methylbenzotriazole 0.2 g   Boric acid 8g   40 g of diethylene glycol   8-mercaptoadenine 0.3 g KOH was added so that the pH of the working solution was 10.4.

[0304] (Fixer composition) Per 1 liter of solution used   Ammonium thiosulfate (70% aqueous solution) 200 ml   Sodium sulfite 22g   Boric acid 9.8g   Sodium acetate trihydrate 34g   Acetic acid (90% aqueous solution) 14.5 g   Tartaric acid 3.0g   Aluminum sulfate (27% aqueous solution) 25 ml The pH of the liquid used was adjusted to 4.9 with sulfuric acid.

The followings were evaluated for the obtained samples.

(Processing conditions) (Process) (Temperature) (Time) Current image 35 ° C. for 30 seconds Fixing 35 ° C. for 20 seconds Water washing Normal temperature 20 seconds Squeeze / dry 50 ° C. for 30 seconds Total 100 seconds (sensitivity, gamma Evaluation) Step wedges are closely attached,
Using a filter with a wavelength of 633 nm as a substitute for HeNe laser light, exposure was performed for 1.5 × 10 ^-7 seconds with a high-illuminance photometer, and under the above-mentioned development conditions, an automatic processor G manufactured by Konica G
Treated with R-27. The developed sample obtained is PD
It was measured with A-65 (Konica Digital Densitometer).

The sensitivities in the table below are for sample No. A concentration 2.
It is expressed as a relative sensitivity when the sensitivity in 5 is 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0, and it is shown that an ultrahigh contrast image can be obtained only when the gamma value in the table is 10 or more.

(Evaluation of Scratches) After conditioning the sample for 60 minutes under the condition of 23 ° C. and RH of 48%, the sample before treatment was treated with a commercially available nylon scrubbing brush for 2 × with respect to a sample of 3.5 cm × 30 cm. Applying a load of 300 g per 2 cm area,
The sample was rubbed at a speed of 30 cm per second. Then, development processing was performed in the same manner as above, and the scratch level was visually evaluated according to the following criteria.

5: No scratches at all 4: Slight scratches were blackened 3: Slight density but scratches were blackened overall but practically lower limit level 2: Blackening density was considerably high, scratches were scratched overall There is blackening. Level 1 which poses a problem on the market: Level at which practical use is not possible (evaluation of cracks) The samples were left in an absolutely dry state at 55 ° C for 3 days, and then the cracks were visually evaluated according to the following criteria.

(Evaluation of curl) A sample of 30 cm × 30 cm after the treatment was placed on a horizontal desk and evaluated by the rising of the four corners of the treatment. The higher the rise (numerical value), the more curls there are and the more difficult it is to use.

(Evaluation of Drying Property) At the time of processing the sample, the condition coming out of the drying part was visually evaluated according to the following criteria.

5: Completely dry 4: Slightly wet, but samples do not stick to each other 3: Wet but practically lower limit level 2: Very wet, samples stick to each other Problem level 1: Table 1 below shows the evaluation results of a level not lower than practical use.

[0313]

[Table 1]

As is clear from the results shown in Table 1, the samples of the present invention have excellent sensitivity and gamma, and have few scratches and cracks. Further, the sample of the present invention had less curl as compared with the comparative sample, and the drying property during the development processing was good.

Example 2 The following Samples E to G were prepared in the same manner as in Example 1.

The coated silver amount of the sample was 3 g / m ² .

Sample No. C: Simultaneous coating of a gelatin subbing layer of Formulation 1, a silver halide emulsion layer of Formulation 2 thereon, a silver halide emulsion layer of Formulation 3 thereon, and a protective layer of Formulation 4 thereon, a total of four layers ( Same composition as Sample C of Example 1 (however, the gelatin amount of each of Formula 1, Formula 2, Formula 3, and Formula 4 was 0.45 g, 0.65 g, 0.65 g, and 1.3 per m ² respectively.
g: 3.05 g / m ² in total) E: (Comparative sample) In Sample C, the gelatin amounts of Formula 1, Formula ^2, Formula 3, and Formula 4 were 0.8 g and 0.8 g per 1 m ^2, respectively. 0.8g, 2.0g total 4.4
g / m ^2, and the same F: (Comparative sample) in Sample C, the gelatin amounts of Formula 1, Formula 2, Formula 3, and Formula 4 were 0.1 g, 0.2 g, and 0 per 1 m ^2, respectively. 0.2g, 0.5g in total 1. 0
g / m ² and the same G except for the following: in Sample C, the amount of gelatin in each of Formula 1, Formula 2, Formula 3 and Formula 4 is 0.3 g per 1 m ^2, respectively.
0.3g, 0.3g, 0.7g total 1. Table 2 below shows the results of evaluation of the sample obtained in the same manner as in Example 1 except that the amount was 6 g / m ² .

[0318]

[Table 2]

From Table 2, the samples of the present invention were excellent in scratch resistance, crack resistance and curl. Further, the drying property during the development processing was also good.

Example 3 In the same manner as in Example 1, the following samples H, I, H ',
I'was created.

Sample No. H: A sample was prepared in the same manner as in the sample C of Example 1 except that the spectral sensitizing dyes of Formula 2 and Formula 3 were changed to D-1 below. For the exposure, a sample was prepared in the same manner as in Example 1, except that the spectral sensitizing dyes of Formula 2 and Formula 3 in the sample C of Example 1 were changed to D-2 below. The exposure was performed using a 670 nm filter H ': The same as sample H except that composite latex PL-10 was removed from sample H above I': sample except that composite latex PL-10 was removed from sample I above Same as I Spectral sensitizing dye D-1 (Exemplary II-1) Spectral sensitizing dye D-2 (Exemplary III-3) The obtained results are shown in Table 3 below.

[0322]

[Table 3]

Example 4 Sample No. 1 of Example 1 In the constitution of D, the following samples J-1 to J-13 were prepared in the same manner except that the amounts of the composite latex and gelatin were changed as shown in Table 4 below.

[0324]

[Table 4]

The results of evaluation of the obtained sample are shown in Table 5 below.

[0326]

[Table 5]

As is clear from the table, all of the samples in which the coating amount of the present invention was the ratio of the composite latex and the gelatin amount had good film physical properties, and the drying property was comparable. It was

Example 5 Samples K-1 to K-4 were prepared by changing the coating solution pH to which the composite latex of the present invention was added, as in the sample H of Example 3 above, as follows.

Sample No. pH K-1: 6.5 K-2: 4.2 K-3: 5.2 K-4: 3.8 The results of evaluation of the obtained samples are shown in Table 6 below.

[0330]

[Table 6]

As is clear from Table 6, the coating solution p of the present invention
The sample by H was superior in various performances to the comparison.

Example 6 Sample L-1 obtained by adding a hardening amount of a hydrazine derivative and a redox compound to Sample H of Example 3 above.
~ L-4 was created.

Sample No. L-1: No hydrazine compound L-2: hydrazine compound (exemplary H-3) L-3: No DIR compound L-4: DIR compound (exemplification No. 25) The results of evaluation of the obtained sample are shown below.

[0334]

[Table 7]

As is clear from Table 7, the samples of the present invention did not show any deterioration in various performances even when the hydrazine derivative and the redox compound were contained in a high contrast amount.

Example 7 Samples M-1 to M3, M-5 to 8 and M were made in the same manner as in the structure of sample C of Example 1 except for the following changes.
-11 and M-13 to 14 were prepared.

Sample No. M-1: (excluding silicone oil) M-2: 30 mg / m ^{2 of} L-21 exemplified as a slip agent was used M-3: L-21 exemplified as a lubricant + PL-2 (complex latex) exemplified was used as a formulation 4. 800 mg / m ² used M-5: MW 40,000 dextran as a water-soluble polymer to formulation 2 0.3 g / m ² used M-6: MW 1,000 dextran as a water-soluble polymer to formulation 2 0.3 g / m ² Use M-7: (excluding latex) M-8: PL-2 as latex 500m to formulation 4
Use g / m ² M-11: Exemplified LF as lipophilic component to formulation 4
Use of 75 g / m ² M-13: (excluding polymethylmethacrylate) M-14: Amorphous silica as matting agent (particle size 8 μm)
It is shown below the results of evaluation in the same manner as 12.5 mg / m ² using Example 1.

[0338]

[Table 8]

Example 8 For the sample prepared in Example 4, the total treatment time (Dry
Time to dry is 45 seconds (development: 15 seconds, fixing 1
The results of treatment for 0 seconds, 10 seconds of washing with water, and 10 seconds of drying are shown in Table 9 below.

[0340]

[Table 9]

As can be seen from the table, the sample of the present invention does not show deterioration in photographic performance and scratch and crack resistance which are the objects of the present invention even in rapid processing, and is excellent in curling degree and drying property after film processing. Was there.

[0342]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material which is excellent in scratch resistance and crack resistance of a film, curl before and after processing and which is easy to use can be obtained. . Further, according to the present invention, a method for processing a silver halide photographic light-sensitive material having a fast drying speed in a rapid processing can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03C 1/43 G03C 1/43 5/29 501 501 5/29 501 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/04 501 G03C 1/047 G03C 1/06 501 G03C 1/12 G03C 1/38 G03C 1/43 G03C 5/29 501

Claims (7)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a layer structure of 3 to 10 layers on a support, at least one of which is a light-sensitive silver halide emulsion layer and at least 1
The layer is a hydrophilic colloid layer, the photosensitive silver halide emulsion layer has a spectral sensitization maximum at 600 to 900 nm, and the photosensitive silver halide emulsion layer and / or the hydrophilic colloid layer is coated. At the time of setting, a composite latex composed of inorganic particles and a hydrophobic polymer is contained in the coating liquid,
The coating solution has a pH of 4.0 to 6.9, and
The total gelatin coating amount on the photosensitive silver halide emulsion layer side is 1.
0-3.6 g / m ² and said hydrophilic colloid
At least one latex in the layer is incorporated into the photosensitive halogen
The total gelatin coating amount (A) on the silver halide emulsion layer side and the composite latte
The silver halide photographic light-sensitive material is characterized in that the total coating amount (B) of the casks contains an amount satisfying the following formula [1] . Formula [1] 1.0 ≦ (A) / (B) ≦ 17.5 2. At least 1 in the hydrophilic colloid layer
The composition according to claim 1, characterized in that it contains a kind of slip agent.
Silver halide photographic light-sensitive material. 3. At least 1 in the hydrophilic colloid layer
15. A water-soluble polymer of a species.
1. The silver halide photographic light-sensitive material as described in 1 or 2. 4. At least 1 in the hydrophilic colloid layer
4. A matting agent according to claim 1, wherein the matting agent is contained.
The silver halide photographic light-sensitive material according to any one of 1. 5. The method according to any one of claims 1 to 4.
In the light-sensitive silver halide emulsion layer of a silver halide photographic material
And / or a hardened amount of hydrazine in the hydrophilic colloid layer
Photographic image of silver halide characterized by containing a derivative
Light material . 6. The method according to any one of claims 1 to 5.
In the light-sensitive silver halide emulsion layer of a silver halide photographic material
And / or a hardened amount of hydrazine in the hydrophilic colloid layer
Releases the development inhibitor by being oxidized with the derivative
Redox DIR compound
Silver halide photographic light-sensitive material . 7. The method according to any one of claims 1 to 6.
The pH of the developer is 9.5 after exposing the silver halide photo-sensitive material.
Hardness of gamma 10-30 by processing at ~ 11.0
Silver halide photography characterized by forming tonal images
Image forming method of photosensitive material.