JPH06175254A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To eliminate the defect that a silver halide photographic sensitive material containing a hydrazine derivative becomes soft with time to generate black spot on an unexposed part. CONSTITUTION:In a silver halide photographic sensitive material having at least one layer of silver halide emulsion layer on a supporting body, a water soluble or dispersible compound which is a compound formed by the addition reaction of active hydrogen with polyisocyanate group, contains at least two free isocyanate group in the molecule, is made by blocking at least >=2 free isocyanate group with bisulfite and furthermore blocking all the remainding isocyanate group with another blocking agent, is contained in at least one layer of the constituting layers of the silver halide photographic sensitive material and the hydrazine derivative is contained in the silver halide emulsion layer and/or the adjacent layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material suitable for photoengraving and capable of reproducing an ultrahigh contrast image, a processing method and a processing agent therefor.

[0002]

2. Description of the Related Art A photolithography process includes a process of converting a continuous tone original into a halftone dot image. In this step, a technique based on infectious development has been used as a photographic technique capable of reproducing an ultrahigh contrast image.

The lith-type silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of about 0.2 μm, a narrow particle size distribution, a well-shaped particle, and a high silver chloride content ( (At least 50 mol%) silver chloride emulsion is used. Such a lith-type silver halide photographic light-sensitive material is treated with an alkaline hydroquinone developer having a low sulfite ion concentration,
By processing with a so-called lith developer, an image with high contrast, high sharpness and high resolution can be obtained. However, since such a lith-type developer is susceptible to aerial oxidation and thus has extremely poor preservability, it is difficult to keep the development quality constant during continuous use.

On the other hand, there is known a method of rapidly obtaining a high-contrast image without using a lith-type developer having poor homeostasis. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material contains a hydrazine derivative. According to this technique, a high-contrast image can also be obtained by processing with a developer having good preservative and capable of rapid processing.

[0005]

However, the silver halide photographic light-sensitive material containing a hydrazine derivative has the drawbacks that it becomes softer with time and black spots are generated in the unexposed area.

An object of the present invention is to soften the silver halide photographic light-sensitive material containing a hydrazine derivative with age,
It is an object of the present invention to provide a technique in which a defect that black spots are generated in an unexposed portion is improved.

[0007]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and to form a constituent layer of the silver halide photographic light-sensitive material. At least one layer is a compound formed by an addition reaction of active hydrogen and a polyisocyanate group, and contains at least two free isocyanate groups in the molecule, and at least two or more of the free isocyanate groups are bisulfite. It contains a water-soluble or water-dispersible reactive compound which is blocked with a salt, and all the remaining free isocyanate groups are blocked with another blocking agent, and the silver halide emulsion layer and / or It is achieved by a silver halide photographic light-sensitive material characterized by containing a hydrazine derivative in its adjacent layer.

The present invention will be described in detail below.

First, the hydrazine derivative contained in the silver halide emulsion layer and / or the adjacent layer of the silver halide photographic light-sensitive material of the present invention will be described.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0011]

[Chemical 1]

In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group containing at least one sulfur atom or oxygen atom, R ₂ represents a hydrogen atom, an alkyl group, an aryl group,
Alkoxy group, aryloxy group, amino group, hydrazino group, carbamoyl group, oxycarbonyl group or -OR
Represents a group, R represents an alkyl group or a saturated heterocyclic group,
G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphinato group, a —CO—CO— group, a thiocarbonyl group or an iminomethylene group, and A ₁ and A ₂ are both a hydrogen atom or one of which is a hydrogen atom and the other is substituted or It represents an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the present invention, among these, the following general formula [H-a], [H-b], [H-c] or [H-d] is further used.
Compounds represented by are preferred.

[0014]

[Chemical 2]

In the above general formula [Ha], R ₁₁ and R ₁₂
Is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, butyl group, dodecyl group,
2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (for example, phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-
Methylcyclohexyl group, pyridyl group, 4-propyl-2-
Pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group) and the like, and R ₁₃ is a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (for example, benzyl group, p-methylbenzyl group, methoxy group). Group, an ethoxy group, an ethyl group, a butyl group), R ₁₄ and R ₁₅ each represent a divalent aromatic group (eg, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents L. A divalent linking group (for example, —SO ₂ CH ₂ CH ₂ NH—, —S
_{O 2 NH -, - OCH 2} SO 2 NH -, - O -, - CH = N-) represents,
R ₁₆ represents —NR′R ″ or —OR ₁₇ , and R ′, R ″ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, dodecyl group), phenyl group ( For example, phenyl group, p-methylphenyl group, p-
Methoxyphenyl group), naphthyl group (eg α-naphthyl group, β-naphthyl group) or heterocyclic group (eg unsaturated heterocyclic group such as pyridine, thiophene, furan or saturated heterocyclic group such as tetrahydrofuran, sulfolane) And R ′ and R ″ may form a ring (for example, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

M and n each represent 0 or 1.
When R ₁₆ represents —OR ₁₇ , Y preferably represents a sulfur atom.

[0017]

[Chemical 3]

In the formula, R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), a substituted or unsubstituted phenyl group or a naphthyl group. , Cyclohexyl group, pyridyl group, pyrrolidyl group, substituted or unsubstituted alkoxy group (eg methoxy group, ethoxy group, butoxy group)
Alternatively, it represents a substituted or unsubstituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

In the present invention, R ₂₃ is preferably a hydrogen atom or an alkyl group.

R ₂₄ represents a divalent aromatic group (for example, a phenylene group or a naphthylene group), and Z represents a sulfur atom or an oxygen atom.

R ₂₅ is a substituted or unsubstituted alkyl group,
It represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group and an aryl group.

The hydrazine derivative can be easily synthesized by a known method. For example, JP-A-2-214850.
No. 2, No. 2-47646, No. 2-12237 and the like.

[0023]

[Chemical 4]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or represents a heterocyclic oxy group, R ₃₁ and R
₃₂ may form a ring with a nitrogen atom. When n = 2,
R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₃₁ and R
_At least one of ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. R ₃₃ represents an alkynyl group or a saturated heterocyclic group.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents

R ₃₁ and R ₃₂ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl). Etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₃₁ and R ₃₂ together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

However, when n = 2, at least one of R ₃₁ and R ₃₂ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group. Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₃₃ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Hc] and [Hd] are such compounds. Also includes.

More preferred compounds in the present invention are the compounds of the general formula [Hc] when n = 2, and the compounds of the general formula [Hd].

In the compound of the general formula [Hc] with n = 2, R ₃₁ and R ₃₂ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Representative compounds represented by the above general formula [H] are shown below.

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

Specific examples of the compounds represented by the general formulas [Ha] to [Hd] are given for the hydrazine derivative used in the present invention. Furthermore, among the compounds represented by the general formula [H], Specific examples include the following compounds.

[0045]

[Chemical 14]

Compounds II-7 to II-54 described in JP-A-3-174,143, page 24, upper right column to page 26, lower right column.

The hydrazine derivative used in the present invention is preferably the compound represented by the above general formula [H], but a hydrazine compound represented by the following general formula [H '] may be used.

General formula [H '] R ¹ -NH-NH-R ^{2 In} general formula [H'], R ¹ is quinolyl, pyridyl or cyclohexyl or a group represented by the following formulas (a) to (h) :

[0049]

[Chemical 15]

R ² is a hydrogen atom or a phenyl group, R ³ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms or a sulfonamide group, R ⁴ and R ⁵ are a hydrogen atom or a halogen atom, and R ⁶ has 1 to 4 carbon atoms
Represents an alkyl group or an alkoxy group.

Specific examples of the compound represented by the general formula [H '] are shown below.

[0052]

[Chemical 16]

[0053]

[Chemical 17]

The hydrazine derivative has the general formula [Hc]
Alternatively, when the compound of [Hd] is contained, Japanese Patent Application No. 2-23
No. 4203, page 69, line 1 to page 144, line 12, at least one of the nucleation promoting compounds is used in a silver halide emulsion layer and / or
Alternatively, it is preferably contained in a non-photosensitive layer on the side of the silver halide emulsion layer on the support.

Typical specific examples of the nucleation promoting compound are shown below.

[0056]

[Chemical 18]

[0057]

[Chemical 19]

Still another specific example is Japanese Patent Application No. 2-234203.
Nos. 69 to 72, compounds I-1 to I-26, 73 to 78, compounds II to II-29, 80 to 83
Compounds III-1 to III-25 described on page, Compounds IV-1 to IV-41 described on pages 84 to 90, Compound V-1-1 described on pages 92 to 96 -V-1-27, compounds V-II-1 to V-II-30 described on pages 98 to 103, compounds V-III-1 to V-III described on pages 105 to 111 -35, p. 113-1
Compounds IV-1 to IV-I-44 described on page 21, pages 123 to 1
Compounds VI-II-1 to VI-II-68 and 13 described on page 35
Compounds described on pages 7 to 143 VI-III-1 to VI-III-
There are other than the above-described representative examples in 35.

Specific compounds other than the above are disclosed in
No. 2-841 pp. 542 (4) to 546 (8) include compound examples (1) to (61) and (65) to (75).

The hydrazine derivatives represented by the general formulas [H] and [H '] can be synthesized by the method shown on pages 546 (8) to 550 (12) of JP-A No. 2-841.

The addition position of the hydrazine derivative is the silver halide emulsion layer and / or the adjacent layer. The addition amount is
1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol is preferable per 1 mol of silver, and more preferably 1 × 10 ⁻⁵ to 1 × per 1 mol of silver halide.
It is 10 ^-2 mol.

As the blocking agent used in the present invention, a compound having at least one active hydrogen capable of reacting with a free isocyanate group and an anionic group in the same molecule, for example, oxybenzoic acid, phenolsulfonic acid, glycolic acid. , Lactic acid, malic acid, bisulfite, bicarbonate and the like are used.

Examples of the reactive compound containing a free isocyanate group used in the present invention include those obtained from an excess amount of a polyisocyanate of a compound having two or more active hydrogen groups. Examples of the compound having two or more active hydrogen groups include those having two or more hydroxyl groups, carboxyl groups, amino groups, or mercapto groups at the end or in the molecule, and further polyether, polyester, polyether ester, etc. Is mentioned.

Examples of the polyether include alkylene oxides such as ethylene oxide and propylene oxide,
Alternatively, a polymerization product such as styrene oxide or epichlorohydrin and a random or block copolymer thereof, or an addition polymer to a polyhydric alcohol, etc. may be mentioned.

Polyesters and polyether polyesters include polyvalent saturated and unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid and maleic anhydride, or acid anhydrides thereof, and ethylene glycol, diethylene glycol, 1,3 -And polyhydric saturated and unsaturated alcohols such as 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, polyethylene glycol of relatively low molecular weight , Mainly linear or branched condensates obtained from polyalkylene ether glycols such as polypropylene glycol and mixtures thereof,
In addition, polyesters made from lactones and hydroxy acids, and further polyether esters obtained by adding ethylene oxide, propylene oxide or the like to polyesters produced in advance are also included.

Polyisocyanates for obtaining urethane compounds by reacting with a compound having two or more active hydrogen groups include tolylene diisocyanate isomers,
Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2 Examples thereof include aliphatic diisocyanates such as 1,4-trimethylhexamethylene diisocyanate.

Specific examples (structural formulas) of these polyisocyanates will be given below.

[0068]

[Chemical 20]

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

Examples of the hydroxyl group, amino group or mercapto group are ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol,
Neopentyl glycol, 1,4-cyclohexanedimethanol, glycols such as ethylene oxide adduct of bisphenol A, glycerin, trimethylolpropane,
Mention may be made of polyhydric alcohols such as pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol and water. .

Examples of the carboxy group include succinic acid, adipic acid, sebacic acid, isophthalic acid, terephthalic acid,
5-sulfoisophthalic acid etc. can be mentioned.

The urethane type compound containing at least two free isocyanate groups used in the present invention can be easily synthesized by a conventionally known polyaddition method. In this case, however, the molar ratio of isocyanate group / active hydrogen group can be freely selected to be 1 or more, but it is preferable that the content of free isocyanate group in the obtained urethane compound is 1 to 30% by weight.

Next, the free isocyanate groups of the synthesized urethane compound are blocked with an aqueous bisulfite solution. In addition, examples of the bisulfite salt that is blocked with a compound having one or more active hydrogen groups and anionic salts in the same molecule as necessary include sodium bisulfite, potassium bisulfite, ammonium bisulfite, and the like. Examples of compounds having one or more and anionic salt-like groups or anionic salt-forming groups in the same molecule include amino groups and hydroxyl groups such as aminosulfonic acids, aminocarboxylic acids and hydroxyacetic acid as described above. Sulfonic acid groups, those having two types of groups of carboxylic acid groups are mentioned, as the aminosulfonic acids sulfanilic acid, N-phenylaminomethanesulfonic acid, Taunrin methyl taurine, as the aminocarboxylic acids, glycine, alanine, Glutamic acid, aminobenzoic acid, diaminobenzoic acid and The Dorokishi acid, glycolic acid, lactic acid, malic acid, salicylic acid and the like. Since they are used as a mixture with the bisulfite, they are used as lithium salt, sodium salt, potassium salt, ammonium salt and the like.

Specific synthetic methods for blocking are described, for example, in JP-B-55-39254 and JP-B-53-17642. The reactive urethane compound used in the present invention is commercially available, for example, from Daiichi Kogyo Seiyaku Co., Ltd. under the trade name of Elastron. For example, the following products are available depending on the type of raw material polyol (polyester polyol, polyether polyol, etc.).

Elastron H-3, E-37 (polyester type), Elastron C-9, F-29, C-52, CT-
7, H-38, A-42, BAP, W-11, (polyether type), and Elastron R-24, S-24, KS-18, etc., and in addition, Coronate from Nippon Polyurethane Industry Co., Ltd. 25072515, AX-35, 36 from Koyo Sangyo Co., Ltd. and K-1000 series from Nippon Shokubai Chemical Co., Ltd. Next, specific compound examples will be given, but the present invention is not limited to these.

[0077]

[Chemical formula 23]

[0078]

[Chemical formula 24]

[0079]

[Chemical 25]

[0080]

[Chemical formula 26]

[0081]

[Chemical 27]

Examples of commercially available compounds include:
There are the following.

Elastron H-3 (trade name of Dai-ichi Kogyo Seiyaku Co., Ltd.) Elastron E-37 (〃 〃) Elastron H-38 (〃 〃) Elastron A-42 (〃 〃) Elastron C-9 (〃 〃) Elastron W-11 (〃〃) The amount of the compound used in the present invention can be arbitrarily selected according to the purpose. Normally 0 for dry gelatin.
It can be used in proportions ranging from 01 to 40% by weight. Particularly preferably, it is used in a proportion in the range of 1 to 30% by weight.

The silver halide photographic light-sensitive material of the present invention may have at least one conductive layer on the support. As a typical method for forming the conductive layer, there are a method using a water-soluble conductive polymer, a hydrophobic polymer and a curing agent, and a method using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, pages 5 to 15, can be used. The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention includes silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used for the silver halide emulsions described above can be used, but silver chlorobromide, silver bromide or 4
Silver iodobromide containing silver iodide in an amount of not more than mol%.

The above-mentioned silver halide grains contained in the silver halide emulsion are (standard deviation of grain size) / (average grain size)
Monodisperse particles having a coefficient of variation represented by × 100 of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention.

For example, various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and UV absorbing agents are used in silver halide photographic emulsions and backing layers. Agents, anti-irradiation dyes, heavy metals, matting agents and the like can be further incorporated by various methods.
Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer.

More specifically, these additives are described in Research Disclosure, Vol. 176, Item / 7643 (December 1978).
187 and Item / 8716 (November, 1979), and the corresponding places are summarized in the table below.

Additive type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

[0090]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The obtained emulsion was a cubic monodisperse emulsion having an average grain size of 0.20 μm (variation coefficient of grain size distribution: 9%). It was washed with water and desalted by a conventional method. The pAg at 40 ° C after desalting was 8.0. Subsequently, the following sensitizing dye D was added to this emulsion per mol of silver.
-1 of 200 mg and D-2 of 10 mg were added, and further the mixture of the following compounds [A], [B] and [C] was added, and then sulfur sensitization was carried out to obtain an emulsion A.

[0092]

[Chemical 28]

(Preparation of silver halide photographic light-sensitive material) On one surface of a polyethylene terephthalate support which has been subjected to undercoating,
A photosensitive silver halide emulsion layer having the following formulation (1) is coated so that the amount of gelatin is 2.0 g / m ² and the amount of silver is 3.2 g / m ^2, and the emulsion of the following formulation (2) is further applied thereon. The protective layer has a gelatin content of 1.
By coating so as to be 0 g / m ^2, also the amount of gelatin is 2.4 g / m ² and the backing layer of the following formulation (3) in the support surface of the emulsion layer opposite (already subbing processed) Then, a backing protective layer having the following formulation (4) was further applied thereon so that the amount of gelatin would be 1 g / m ² .

The pH of each layer was adjusted with sodium carbonate and / or citric acid, and the film surface pH of the outermost layer was adjusted.
Photosensitive materials (1) to (4) shown in (4) were prepared.

Formulation (1) (composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3, 3a, 7-Tetrazaindene 30mg / m ² Antifoggant: 5-nitroindazole 10mg / m ² 1-Phenyl-5-mercaptotetrazole 5mg / m ² Surfactant: Sodium dodecylbenzenesulfonate 0.1g / m ²

[0096]

[Chemical 29]

Hydrazine derivative 7 × 10 ⁻⁵ mol / m ²

[0098]

[Chemical 30]

Formulation (3) (backing layer composition)

[0100]

[Chemical 31]

Gelatin 2.4 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 0.1 g / m ² Surfactant: S-1 6 mg / m ² Colloidal silica 100 mg / m ² Hardener: E 55 mg / m ²

[0102]

[Chemical 32]

Formulation (4) (Backing protective layer composition) Gelatin 1 g / m ² matting agent: monodisperse polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m ² Surfactant: S-2 10 mg / m ² hardening agent Glyoxal 25 mg / m ² Hardener: HA-1 35 mg / m ^{2 In} addition to the polyisocyanate compound shown in Table 1 in the formulation (4), 0.1 mmol / m ² was added to the photosensitive material (1). In the same manner as in (4) to (4), photosensitive materials (5) to (1
9) was produced.

Photosensitive materials (1) to (19), 5 sheets each,
After storing at 23 ° C and 50% RH for 24 hours, seal and package (save
I), left as a thermo treatment for ages at 55 ° C for 3 days (preservation II). Attach a step wedge to the sample in the center (third sheet) of the photosensitive material sample under the above two storage conditions,
After exposure with K tungsten light for 5 seconds, processing was carried out under the following conditions using an automatic processor GR-26SR for rapid processing manufactured by Konica Corporation, which was charged with a developing solution and a fixing solution having the compositions shown below.

The processing conditions are as follows.

Developer Formulation (1) Sodium Bisulfite 40g N-Methyl-p-aminophenol sulfate 350mg Ethylenediaminetetraacetic acid disodium salt 1g Sodium chloride 5g Potassium bromide 1.2g Trisodium phosphate 75g 5-Methylbenztriazole 250mg 2-Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Amine compound Am-1 0.5 ml Potassium hydroxide Amount to bring the pH of the working solution to 11.6 At the time of use, water was added to make 1 l.

[0107]

[Chemical 33]

Fixer formulation (1) Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W / V) / V aqueous solution) 15.7 g Gluconic acid (50% W / W aqueous solution) 8.55 g Aluminum sulphate (48% W / W aqueous solution) 13 ml Glutaraldehyde 3 g Sulfuric acid The pH of the used solution is 4.6. Finished

Development processing conditions Process temperature Time image 38 ° C 20 seconds Fixing 38 ° C 20 seconds Water washing 15 ° C normal temperature 15 seconds Drying 40 ° C 15 seconds Each process time includes the wading transport time to the next process.

The concentration of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the relative sensitivity was shown with the sensitivity of Sample No. 1 at a density of 2.5 as 100, and gamma was displayed with the tangent of the density of 0.1 and 2.5. did. A gamma value of less than 6 cannot be used, and a gamma value of 6.0 or more and less than 10.0 still has insufficient hardness. With a gamma value of 10.0 or higher, the image becomes ultra-high contrast and can be used sufficiently.

The black spots in the unexposed area were also evaluated with a magnifying glass of 40 times. The one with no black spots was ranked as the highest rank "5", and the ranks "4", "3", "2" and "1" were sequentially lowered according to the degree of occurrence of black spots and evaluated. . In addition, 3.5 means the middle of 3 and 4, 4.5 means the middle of 4 and 5. Ranks “1” and “2” are levels that are not practically preferable.

The results are shown in Table 1.

[0113]

[Table 1]

From Table 1, a hydrazine derivative is contained in a silver halide emulsion layer of a silver halide photographic light-sensitive material,
Moreover, it can be seen that the inclusion of the polyisocyanate compound in the backing layer can significantly suppress softening and generation of black spots over time.

Example 2 The following sensitizing dye D- was used instead of the sensitizing dyes D-1 and D-2.
3 mg was added per mol of silver, the hydrazine derivative shown in Table 2 was used in place of the hydrazine derivative shown in Table 1, and 3 × 10 ⁻⁵ of the nucleation promoting compound N-10 was added to the formulation (1).
Photosensitive materials (20) to (23) were prepared in the same manner as in the photosensitive materials (1) to (4) except that the addition of mol / m ² was added. Photosensitive materials (24) to (38) were prepared in the same manner as the photosensitive materials (5) to (19) except that the hydrazine derivative was changed to that shown in Table 2. The photosensitive materials (20) to (38) were processed in the same manner as in Example 1 except that the developer formulation was changed to the following developer formulation (2) (Experiment Nos. II-1 to II-19). The results are shown in Table 2.

[0116]

[Chemical 34]

Developer Formulation (2) (Composition A) Pure Water (Ion Exchange Water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzo Triazole 200 ml 1-Phenyl-5-methylcaptotetrazole 30 mg Potassium hydroxide Amount to adjust the pH of the solution to 10.5 Potassium bromide 4.5 g (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 g Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter.

[0118]

[Table 2]

From Table 2, the hydrazine derivative is contained in the silver halide emulsion layer of the silver halide photographic light-sensitive material,
Moreover, it can be seen that the inclusion of the polyisocyanate compound in the backing layer can significantly suppress softening and generation of black spots over time.

[0120]

According to the present invention, the disadvantage that the silver halide photographic light-sensitive material containing a hydrazine derivative becomes softer with time and black spots are generated in the unexposed portion is improved.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one of the constituent layers of the silver halide photographic light-sensitive material is a compound produced by an addition reaction of active hydrogen and a polyisocyanate group, and contains at least two free isocyanate groups in the molecule, and It contains a water-soluble or water-dispersible reactive compound in which at least two or more free isocyanate groups are blocked with bisulfite and all the remaining free isocyanate groups are blocked with another blocking agent. And a silver halide photographic light-sensitive material comprising a hydrazine derivative in the silver halide emulsion layer and / or its adjacent layer.