JP2709756B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material having high sensitivity, and more particularly to a silver halide photographic light-sensitive material having a rapid development progress and improved storage stability.

[0002]

2. Description of the Related Art In general, it is important to improve the development progress of silver halide photographic materials from the viewpoint of increasing sensitivity and speeding up processing. Silver iodobromide emulsions are used for high-sensitivity photographic materials because of the trade-off between sensitivity and image quality. In particular, such emulsions have a slower progression in development than silver chloride and silver bromide. Was a big issue.

As a method for solving this problem, there has long been known a method of adding a nonionic surfactant having a polyoxyethylene group described in US Pat. Nos. 2,423,549, 2,531,832 and 2,533,990 to an emulsion. This technique alone was not sufficient to satisfy the demand for faster processing.

[0004] Also, Japanese Patent Application Laid-Open Nos.
44025, JP-A-56-156826 and JP-B-48-43136, it has been known that the development proceeds in the presence of a cationic compound when the development proceeds. However, these cationic compounds are liable to be accompanied by fog, and have a drawback that fog increase is conspicuous particularly during long-term storage.

The ThJames, The Th, as a fog inhibitor
eory of the Photographic Process (4th edition 1977) 396
On pages 399 to 399, compounds such as nitrobenzimidazole, mercaptotetrazole, benzotriazole and tetrazaindene are described, but these compounds have the drawback of suppressing fog and lowering the sensitivity of silver halide emulsions.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having improved development progress and improved fog increase during long-term storage.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having at least one silver halide photographic light-sensitive layer on at least one side of the support. In the non-photosensitive layer on the same side, at least one cationic compound containing a quaternary nitrogen represented by the following general formulas (Ia) and (Ib) and at least one compound represented by the general formula (II) Both could be achieved by including one in the same layer or each in a separate non-photosensitive layer. General formula (Ia)

[0008]

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Formula (Ib)

[0010]

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In the formula, R ₁ is an alkyl group having ₁ to 26 carbon atoms, an alkenyl group having 3 to 26 carbon atoms or- ⁺ N-R
_{2 represents a} (R ₃ ) (R ₄ ) group or a hetero group containing a quaternary nitrogen.
A represents a divalent linking group. R ₂ , R ₃ and R ₄ represent an alkyl group or a substituted alkyl group. Z represents an atom necessary for forming a hetero ring. P represents 1 or 2, and X represents an anion.

Preferred cationic compounds are those having a hydrophobic group of 3 to 18 carbon atoms, particularly preferably 6 to 1 carbon atoms.
8 containing an alkyl group, an alkenyl group, or an alkylene group. General formula (II)

[0013]

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In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, and each is a hydrogen atom; an unsubstituted or substituted which may have a ring or branch having 1 to 20 carbon atoms. Alkyl group; monocyclic or bicyclic unsubstituted or substituted aryl group; unsubstituted or substituted amino group; hydroxy group; alkoxy group having 1 to 20 carbon atoms;
A carbamoyl group which may be substituted with an aliphatic group or an aromatic group; a halogen atom; a cyano group, a carboxy group; an alkoxycarbonyl group having 2 to 20 carbon atoms;
Or a heterocyclic residue containing a 5- or 6-membered ring having a heteroatom such as a nitrogen atom, an oxygen atom and a sulfur atom. R ⁵ and R ⁶ or R ⁶ and R ⁷ may together form a 5- or 6-membered ring. However, at least one of R ⁵ and R ⁷ represents a hydroxy group.

The compound of the general formula (Ia) or the general formula (Ib) according to the present invention may be contained in any layer constituting the silver halide photographic material. Is most preferably added to the non-photosensitive layer.

It is well known that the compound of the formula (II) is used as a physical inhibitor at the time of silver halide grain formation, a stabilizer or a fog inhibitor at the time of chemical ripening and / or immediately before coating. However, it is accompanied by desensitization as a side effect. Normally, silver halide is more sensitive to fog as the sensitivity is increased. If the amount of this compound in the silver halide emulsion is increased to suppress the fog, desensitization of side effects cannot be ignored and this limits the sensitivity.

The sensitivity and fog obtained by incorporating both the cationic compound containing a quaternary nitrogen and the compound of the general formula (II) into the non-photosensitive layer can be obtained by combining one or both compounds with silver halide. Remarkably good results could be obtained as compared with the case where the compound was contained only in the composition. The cationic compound containing a quaternary nitrogen can be used in the range of 10 ^-7 to 10 ^-3 mol / m ² , and is preferably added in the range of 10 ^-6 to 2 × 10 ^-4 mol / m ^2. Good. As an addition method, it may be directly dispersed in a hydrophilic colloid, or may be added after dissolving in water or an organic solvent such as methanol or ethylene glycol. The compound of the general formula (II) is contained in a non-photosensitive hydrophilic colloid solution per mole of silver halide of a light-sensitive material containing the compound.
^It is desirable to add in the range of ^{-3 to} 2 × 10 ^-2 mol / m ² .

Next, specific examples of the compounds represented by the formulas (Ia) and (Ib) are shown.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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Next, specific examples of the compound represented by formula (II) will be shown.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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As the photosensitive silver halide used in the present invention, specifically, silver chloroiodide, silver iodobromide, silver chloroiodobromide, silver chloride, silver bromide, and silver chlorobromide can be used. it can. Preferably, silver iodobromide is used. Here, the content of silver iodide is preferably in the range of 3 to 30 mol%, particularly preferably 7 to 20 mol%. The average particle size is preferably at least 0.5 μm. The particle size distribution may be narrow or wide. The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral, or irregular such as spherical or plate-like.
It may have a crystalline form or a composite form of these crystalline forms. It may consist of a mixture of particles of different crystal forms. Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention. Regarding such tabular grains, U.S. Pat.
No. 4,434,227 and JP-A-58-127921.

The photosensitive silver halide emulsion used in the present invention is described in P. Grafkides, "Shimmy
A Physique Photography (Chimie et Ph
ysique Photographique) "(Paul Montell Paul
Published by Montel, 1967), GF Duffin (G.
F. Duffin), "Photographic Emulsion Chemistry"
(The Focal Press, 1966
), VLZelikman et al.
al) Making and Coating Photogrgr Emulsion
aphic Emulsion) "(Focal Press The Focal P
ress, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. .

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be used as a mixture.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts and the like may be present in the course of silver halide grain formation or physical ripening. Good.

As the light-sensitive silver halide emulsion, a so-called unprimed emulsion which does not undergo chemical sensitization can be used, but is usually chemically sensitized. For chemical sensitization, see, for example, H. Frieser, ed. “Day Grandlägen der Photograph Ischen Protesse Mitt Silberhalogeniden (Di)
e Grundlagen der Photographischen Prozesse mit sil
ber-halogeniden) "(Academiche Feerlag)
Akademische Verlagsgesllschaft., 1968) 675 〜
The method described on page 734 can be used. That is,
Sulfur sensitization using a compound containing sulfur or active gelatin that can react with iron ions, reduction sensitization using a reducing substance,
A noble metal sensitization method using gold or another noble metal compound can be used alone or in combination. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and the like can be used. For the noble metal sensitization, complex salts of metals of Group VIII of the periodic table, such as platinum, iridium, and palladium, can be used in addition to gold complex salts.

Various compounds can be added to the above-mentioned photosensitive silver halide emulsion in order to prevent a decrease in sensitivity and generation of fog during the production process, storage or processing of the photosensitive material. Those compounds are 4-hydroxy-6-methyl-
Including 1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds,
An extremely large number of compounds such as mercapto compounds and metal salts have been known for a long time. One example of a compound that can be used is
K. Mess, The Theory of the Photographi Process
c Process) (Third Edition, 1966), with the original documents listed therein, as well as JP-A-49-81024, JP-A-50-6306, and JP-A-50-6306.
Any of the antifoggants described in US Pat. No. -19429 and U.S. Pat. No. 3,850,639 can be used.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer comprising a hydrophilic colloid, and the hydrophilic colloid used is the same as described above. Further, the protective layer may be a single layer or a multilayer.

A matting agent used in the light-sensitive material of the present invention,
Various additives such as a slipping agent, a hydrophilic colloid, a polymer latex, a gelatin hardener, a dye, a surfactant, an antistatic agent, and a spectral sensitizing dye, a support, a method for producing the support and the photosensitive material of the present invention, and a developing method. There is no particular limitation on the description, and the description in JP-A-62-133448 and the description in Research Disclosure, Item 17643 (December 1978) or Item 18716 (November 1979) can be referred to. it can.

The relevant portions of these research disclosures are summarized in the following table.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648 right column to supersensitizer 649, right column 4 Brightener page 24 5 Antifoggant page 24-25 page 649 right column and stabilizer 6 Light absorber, f 25-26 page 649 right column to filter dye 650 page left column Ultraviolet absorber 7 stain inhibitor page 25 Right column, page 650, left to right column 8 Dye image stabilizer, page 25 9 Hardening agent, page 26, page 651, left column 10 Binder, page 26 Same as above 11 Plasticizer, lubricant 27 page 650, right column 12 Coating aid, surface 26- Page 27 Same as above Activator 13 Antistatic agent Page 27 Same as above 14 Color coupler page 28 Page 647-648

[0044]

Next, the present invention will be specifically described based on examples. Example 1 (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring, and a plate-like silver iodobromide having an average grain size of 1 µm (average iodine was added). (Content 10 mol%). Thereafter, the emulsion was washed with water by a usual precipitation method, and then chemically sensitized by a gold-sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A. Sensitizing Dye-1 was added before chemical sensitization. Silver halide emulsion A
Emulsion B (average iodine content 6 mol%) was prepared in the same manner as described above except that the amount of potassium iodide and the preparation temperature were adjusted. Sensitizing dye-1 3.0 mg / Ag1g

[0045]

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(2) Preparation of Coated Samples Samples 1 to 12 were prepared by sequentially providing layers of the following formulation on a triacetyl cellulose support from the support side. (Lower layer) Binder: Gelatin 1 g / m ² Dye: 10 ^-4 mol / m ²

[0047]

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Additives: compounds of general formula (I) and / or general formula (II) (listed in Table 1)

(Intermediate Layer) Binder: Gelatin 0.4 g / m ² Coating Aid: Poly-p-styrenesulfonic acid potassium salt 8 mg / m ² Additive: Compound of general formula (I) and / or general formula (II) ( (See Table 1)

(Emulsion layer) Silver coating amount: Emulsion A 6.3 g / m ² Binder: Gelatin 1.6 g / Ag 1 g Dextran (MW about 40,000) Trimethylolpropane 400 mg / m ² Coating aid: 1 mg of potassium poly-p-styrenesulfonate / M ² additive: compound of general formula (I) and / or general formula (II) (described in Table 1)

(Surface protective layer) Binder: Gelatin 0.7 g / m ² Coating aid: 12 mg / m ²

[0052]

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Antistatic agent 2 mg / m ²

[0054]

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Hardening agent: 1,2-bis (vinylsulfonylacetamide) ethane 2.3 × 10 ⁻⁴ mol / m ² Matting agent: polymethyl methacrylate fine particles (average particle size 3 μ) 0.13 mg / m ²

(3) Storage stability test An unexposed sample was placed in a container capable of shielding light and easily replacing air, and was kept in a thermo-hygrostat maintained at a temperature of 50 ° C. and a relative humidity of 70% for 7 days. After storage, 26.5 ° C 4ft / m using a combination of HPD, developer (Fuji Photo Film Co., Ltd.) and Versamat 5AN automatic developing machine (Kodak, USA).
It was evaluated as a fog value after development processing in.

[0057]

[Table 1]

As can be seen from Table 1, in the samples in which the compounds (I) and (II) were added to the lowermost layer or the intermediate layer, which is a non-photosensitive layer, either one or both of the two compounds were added to the emulsion layer. It can be seen that the fog is small irrespective of the higher sensitivity as compared with the sample added to the sample.

Example 2 The sample of Example 1 was naturally aged for 100 days, and then treated with the following developer for 20 days.
5 'and 10'. 1 liter was added a developer Metol 2g Sodium sulfite 100g Hydroquinone 5g borax · 10H ₂ O 2g Water

[0060]

[Table 2]

As can be seen from Table 2, the development of the sample of the present invention is faster than that of the control and comparative samples, that is, the fog is small even though the relative sensitivity is particularly high at a short developing time of 5 '. I understand.

Claims (1)

(57) [Claims] At least one side of at least one side of the support
In a silver halide photographic light-sensitive material having a silver halide photographic light-sensitive layer, the non-light-sensitive layer on the side where the light-sensitive layer is located with respect to the support is represented by the general formula (Ia) or (Ib): Silver halide light-sensitive material characterized in that at least one kind of cationic compound containing secondary nitrogen and at least one kind of the compound represented by formula (II) are contained in the same layer or in respective non-light-sensitive layers. . Formula (Ia) General formula (Ib) In the formula, R ₁ is an alkyl group having ₁ to 26 carbon atoms,
26 alkenyl groups or- ⁺ NR ₂ (R ₃ ) (R ₄ ) groups,
Represents a hetero group containing a quaternary nitrogen. A represents a divalent linking group. R ₂ , R ₃ and R ₄ represent an alkyl group or a substituted alkyl group. Z represents an atom necessary for forming a hetero ring. P represents 1 or 2, and X represents an anion. General formula (II) In the formula, R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group,
An aryl group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, an optionally substituted carbamoyl group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, or a hetero substituent;
₅ and R ₆ or R ₆ and R ₇ may form a 5- or 6-membered ring. However, at least one of R ₅ and R ₇ represents a hydroxy group.